Palladium catalyst composition

ABSTRACT

The present invention discloses 1) a catalyst composition consisting of a crosslinked organic polymer compound and a palladium catalyst, wherein said catalyst is physically carried on said crosslinked organic polymer compound, 2) a manufacturing method of the above catalyst composition 1), characterized by homogenizing a straight chain organic polymer compound, having a crosslinkable functional group, and a palladium catalyst in a solvent dissolving said straight chain organic polymer compound, then depositing a composition thus formed and subjecting the crosslinkable functional group in said deposit to a crosslinking reaction, 3) a method for substitution reaction at an allyl position, characterized by reacting an allyl carbonate and a neucleophilic agent in the presence of the above catalyst composition 1), and 4) a method for oxidizing an alcohol, characterized by subjecting the above catalyst composition 1) to reaction with an alcohol. The catalyst composition of the present invention can be safely and easily handled without danger of spontaneous ignition, and the like, and is extremely useful as a catalyst for various chemical reactions, and further activity thereof is not decreased by repeated use thereof and a metal catalyst does not leak from a polymer compound which is a carrier thereof.

TECHNICAL FIELD

The present invention relates to a catalyst composition comprising apalladium catalyst carried on a crosslinked organic polymer compound,which has superior solvent resistance and keeps activity thereof inrepeated use.

BACKGROUND OF THE INVENTION

Palladium is known as a useful catalyst since it induces variousconversion reactions in organic synthesis. However, this metal has manyproblems in direct use as a catalyst because it is expensive and inaddition, it loses partially its activity on contact with air and cannotbe used repeatedly. Fixation of palladium on a polymer as a technologyto solve these problems has been attempted and various reactions usingpalladium fixed on a polymer have been reported frequently so far.However, any of conventional palladium fixed on a polymer still has acommon problem that catalyst recovery rate is low and activity decreasesin repeated use, although stability of the catalyst itself is improved.

For example, the present inventors created a microcapsulated metalcatalyst by fixing a palladium compound such as a palladium complexcompound, an organic palladium compound, an inorganic salt and anorganic salt, on a polystyrene-type compound, a polymer compound havingan aromatic ring (for example, see the specification of Japaneseapplication; JP-2001-59742). However, the above microcapsulated metalcatalyst turned out to be difficult to use for a reaction employing ageneral organic solvent, because any of polymer compounds used ascarriers is a non-crosslinked type and has defect of easily dissolvingin an organic solvent to be used for a common organic reaction, such asmethylene chloride, tetrahydrofuran, benzene and toluene. Because thepolymer compound to be used as a carrier of the above microcapsulatedmetal catalyst was a non-crosslinked type, said metal-catalystcomposition agglomerated easily, resulting in smaller surface area ofsaid metal-catalyst composition, which caused a problem of very lowcatalyst efficiency due to smaller amount of actually functioningcatalyst compared with an amount of the metal carried on a polymercarrier. Another problem was that raw materials or reaction productswere caught into a carrier polymer constituting a catalyst compositionin a reaction using these metal catalysts.

To solve these problems, the present inventors studied use of acrosslinked polymer carrier obtained by crosslinking with divinylbenzeneor the like, as the above polystyrene-type polymer compound. However, itturned out to be impossible to fix a metal on polystyrene crosslinked bydivinylbenzene, which is insoluble in a general organic solvent, becauseit was necessary to dissolve a polymer carrier in a solvent in order forthe polymer to carry the metal physically.

On the other hand, a method for fixing a metal catalyst on a crosslinkedpolymer to which an ion-exchange group is introduced has been known as amethod for fixing a metal catalyst on such a crosslinked polymer carrier(see Jp-A-59-27840, for example). However, a metal catalyst carried on acarrier obtained by such a method was sometimes difficult to userepeatedly due to leakage of the carried metal catalyst depending onproperties of liquid to be used with.

In such situations, a more versatile new metal catalyst carried on acrosslinked polymer wherein the polymer carrier is insoluble in anorganic solvent and the carried metal hardly leaks and can keep itsactivity in repeated use has been required.

SUMMARY OF THE INVENTION

The present invention provides 1) a catalyst composition comprising acrosslinked organic polymer compound and a palladium catalyst, whereinsaid catalyst is physically carried on said crosslinked organic polymercompound, 2) a manufacturing method of the above catalyst composition1), characterized by homogenizing a straight chain organic polymercompound having a crosslinkable functional group and a palladiumcatalyst in a solvent dissolving said straight chain organic polymercompound, then depositing a composition thus formed and subjecting thecrosslinkable functional group in said deposit composition to acrosslinking reaction, 3) a method for substitution reaction at an allylposition, characterized by reacting an allyl carbonate and aneucleophilic agent in the presence of the above catalyst composition1), and 4) a method for oxidizing an alcohol, characterized bysubjecting the above catalyst composition 1) to reaction with analcohol.

That is, the present inventors have found, after intensive study toattain the above objectives, that by homogenizing a straight chainorganic polymer compound having a crosslinkable functional group and apalladium catalyst in a solvent dissolving said straight chain organicpolymer compound, then depositing a composition formed and subjectingthe crosslinkable functional group in said deposit composition to acrosslinking reaction, a catalyst composition can easily be prepared,which comprising a crosslinked organic polymer compound and a palladiumcatalyst, wherein said catalyst is physically carried on saidcrosslinked organic polymer compound. The inventors have further foundthat thus obtained catalyst composition has higher activity thanconventional palladium catalysts in various reactions and superiorsolvent resistance, leading to durable activity even in repeated use, aswell as is easily handled, and thus the present invention has beencompleted. In addition, after further intensive study, the presentinventors have found that by homogenizing a straight chain organicpolymer compound of particular structure having a crosslinkablefunctional group and Pd(0) coordinated by a ligand, in a solventdissolving said straight chain organic polymer compound, then depositinga composition formed and subjecting the crosslinkable functional groupin said deposit composition to a crosslinking reaction, a catalystcomposition where Pd(0) not coordinated by a ligand is physicallycarried can also be synthesized easily, and thus the present inventionhas been completed

BEST MODE FOR CARRYING OUT OF THE INVENTION

A palladium catalyst relating to the present invention includes anycompound as long as it can be used as a palladium catalyst in thisfield, and a compound derived from Pd(0), Pd(I) and Pd(II) ispreferable. A compound derived from Pd(0) includes Pd(0) itself (havingno ligand, etc.) and a Pd(0) complex coordinated by a ligand. A compoundderived from Pd(I) includesdichloro-μ-bis[bis(dimethylphosphino)methane]dipalladium(Pd₂Cl₂[(CH₃)₂PCH₂P(CH₃)₂]₂),dichloro-μ-bis[bis(diphenylphosphino)methane]dipalladium(Pd₂Cl₂[Ph₂PCH₂PPh₂]₂), etc., and a compound derived from Pd(II)includes, for example, a Pd(II) salt such as halogenated Pd(II)(chloride, bromide, iodide, etc.), Pd(II) carboxylates, (acetate,propionate). Among these, Pd(0) and a Pd(II) salt are preferable andPd(0) is more preferable.

A ligand of a Pd(0) complex includes 1,5-cyclooctadiene (COD),dibenzylideneacetone (DBA), bipyridine (BPY), phenanthroline (PHE),benzonitrile (PhCN), isocyanide (RNC), triethylarsine (As(Et₃)), organicphosphine ligands such as dimethylphenylphosphine (P(CH₃)₂Ph),diphenylphosphinoferrocene (dPPf), trimethylphosphine (P(CH₃)₃),triethylphosphine (P(Et)₃), tri-tert-butylphosphine (P(^(t)-Bu)₃),tricyclohexylphosphine (PCy₃), trimethoxyphosphine (P(OCH₃)₃),triethoxyphosphine (P(OEt)₃), tri-tert-butoxyphosphine (P(O^(t)-Bu)₃),triphenylphosphine (PPh₃), 1,2-bis(diphenylphosphino) ethane (DPPE),triphenoxyphosphine (P(OPh)₃), etc. Among these, an organic phosphineligand, particularly triphenylphosphine, tri-tert-butylphosphine,triethylphosphine, trimethylphosphine, and the like are preferable.Among these, triphenylphosphine is more preferable. When a palladiumcatalyst carried on a catalyst composition of the present invention isPd(0) having ligands, the number of the ligands is usually 1 to 4,depending on kinds of straight chain organic polymer compounds used inpreparation, crosslinking reaction conditions, etc.

A crosslinked organic polymer compound includes, for example, acrosslinked compound of a polymer or a copolymer obtained bypolymerizing or copolymerizing one or more kinds of 1) monomers having acrosslinkable functional group and a polymerizable double bond, and acrosslinked compound of a copolymer obtained by copolymerizing one ormore kinds of 1) monomers having a crosslinkable functional group and apolymerizable double bond and one or more kinds of 2) monomers having apolymerizable double bond. Among these compounds, a crosslinked compoundof a copolymer obtained by copolymerizing two kinds of 1) monomershaving a crosslinkable functional group and a polymerizable double bondand one kind of 2) monomer having a polymerizable double bond ispreferable.

A crosslinkable functional group includes, for example, a condensablegroup by a condensation reaction such as dehydration condensation byadding an acid or heating and a reactable group with a suitablecrosslinking agent, and specifically includes an epoxy group, a carboxylgroup, a hydroxyl group, an acyloxy group, an isocyanate group, an aminogroup, etc.

A monomer unit constituting a copolymer before crosslinking the abovecrosslinked organic polymer compound is a monomer unit derived from amonomer having a crosslinkable functional group and a polymerizabledouble bond, or a monomer unit derived from a monomer having apolymerizable double bond.

Ratio of a monomer unit derived from a monomer having a crosslinkablefunctional group and a polymerizable double bond, to the whole copolymerbefore crosslinking, in a crosslinked organic polymer compound relatingto the present invention, is usually 0.1 to 100% by mol, preferably 1 to50% by mol, more preferably 5 to 40% by mol and still more preferably 5to 20% by mol.

A polymer or a copolymer before crosslinking a crosslinked organicpolymer compound relating to the present invention is a so-calledstraight chain organic polymer compound. A monomer having acrosslinkable functional group and a polymerizable double bond, which isa raw material of the above straight chain organic polymer compound,includes, for example,

(1) a glycidyl compound having an epoxy group as a crosslinkablefunctional group, selected from a glycidyl ether or a glycidyl esterrepresented by the following general formula [1] or [2], respectively:

(wherein R², R³, R⁵ and R⁶ each independently represents a hydrogen atomor an alkyl group having 1 to 6 carbon atoms; X and Y each independentlyrepresents an alkylene group having 1 to 6 carbon atoms; R² may form aring of 3 to 6 members together with carbon atoms of R³ or X, and R⁵ mayform a ring of 3 to 6 members together with carbon atoms of R⁶ or Y; andR¹ and R⁴ each independently is a group represented by the followinggeneral formula [3]:

[wherein R⁷ and R⁸ each independently represents a hydrogen atom or analkyl group having 1 to 6 carbon atoms; R⁹ represents a direct-linkage,an alkylene group having 1 to 6 carbon atoms, an arylene group having 6to 9 carbon atoms, an arylalkylene group having 7 to 12 carbon atoms oran arylenealkylene group having 7 to 15 carbon atoms; and an aromaticring in the above aryl group or aralkyl group may have an alkyl grouphaving 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atomsand/or a halogen atom, as a substituent]),

(2) a monomer having a carboxyl group as a crosslinkable functionalgroup, represented by the following general formula [4]:

(wherein R¹⁰ represents a hydrogen atom or an alkyl group having 1 to 6carbon atoms; R¹¹ represents a hydrogen atom, an alkyl group having 1 to6 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkylgroup having 7 to 12 carbon atoms; and an aromatic ring in the abovearyl group or aralkyl group may have an alkyl group having 1 to 4 carbonatoms, an alkoxy group having 1 to 4 carbon atoms and/or a halogen atomas a substituent; and R¹² represents a direct-linkage, an alkylene grouphaving 1 to 6 carbon atoms, an arylene group having 6 to 9 carbon atoms,an arylalkylene group having 7 to 12 carbon atoms or an arylenealkylenegroup having 7 to 15 carbon atoms), or

(3) a monomer having a hydroxyl group, an acyloxy group, an isocyanatogroup or an amino group as a crosslinkable functional group, representedby the following general formula [5]:

(wherein R¹³ represents a hydrogen atom or an alkyl group having 1 to 20carbon atoms; R¹⁴ represents a hydroxyl group, an amino group,hydroxyalkyl group having 1 to 50 carbon atoms that may have a carbonylgroup and/or an oxygen atom, a hydroxyaryl group having 6 to 10 carbonatoms, a hydroxyaralkyl group having 7 to 50 carbon atoms that may havea carbonyl group and/or an oxygen atom, a hydroxyalkylaryl group having7 to 50 carbon atoms that may have a carbonyl group and/or an oxygenatom, an acyloxy group having 2 to 6 carbon atoms, an arylacyloxy grouphaving 7 to 15 carbon atoms, an isocyanatoalkyl group having 2 to 7carbon atoms, an isocyanatoaryl group having 7 to 20 carbon atoms, anisocyanatoaralkyl group having 8 to 20 carbon atoms, anisocyanatoalkylaryl group having 8 to 20 carbon atoms, an aminoalkylgroup having 2 to 7 carbon atoms, an aminoaryl group having 7 to 20carbon atoms, an aminoaralkyl group having 8 to 20 carbon atoms or anaminoalkylaryl group having 8 to 20 carbon atoms; an aromatic ring inthe above hydroxyaryl group, hydroxyaralkyl group, hydroxyalkylarylgroup, arylacyloxy group, isocyanatoaryl group, isocyanatoaralkyl group,isocyanatoalkylaryl group, aminoaryl group, aminoaralkyl group andaminoalkylaryl group may have an alkyl group having 1 to 4 carbon atoms,an alkoxy group having 1 to 4 carbon atoms and/or a halogen atom; R¹⁵represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7to 12 carbon atoms; and an aromatic ring in the above aryl group oraralkyl group may have an alkyl group having 1 to 4 carbon atoms, analkoxy group having 1 to 4 carbon atoms and/or a halogen atom, as asubstituent)

An alkyl group represented by R², R³, R⁵ and R⁶ in a glycidyl ether or aglycidyl ester represented by the general formula [1] or [2],respectively, which is the above glycidyl compound (1) having an epoxygroup and a polymerizable double bond, may be straight chain, branchedor cyclic and includes a group having usually 1 to 6 carbon atoms,preferably 1 to 4 carbon atoms and more preferably 1 to 2 carbon atoms,and specifically a methyl group, an ethyl group, an n-propyl group, anisopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group,a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentylgroup, a tert-pentyl group, a neopentyl group, an n-hexyl group, anisohexyl group, a sec-hexylgroup, a tert-hexyl group, a cyclopropylgroup, a cyclopentyl group, a cyclohexyl group, etc.

Each of R² and R³ in the general formula [1] is preferably a hydrogenatom, and each of R⁵ and R⁶ in the general formula [2] is preferably ahydrogen atom.

An alkylene group represented by X and Y may be straight chain, branchedor cyclic and includes a group having usually 1 to 6 carbon atoms,preferably 1 to 4 carbon atoms and more preferably 1 to 2 carbon atoms,and specifically includes a methylene group, an ethylene group, atrimethylene group, a propylene group, a methylmethylene group, anmethylethylene group, an ethylmethylene group, a tetramethylene group, apentamethylene group, a hexamethylene group, a cyclopropylene group, acyclopentylene group, a cyclohexylene group, etc.

An alkyl group represented by R⁷ and R⁸ in the general formula [3] maybe straight chain, branched or cyclic and includes a group havingusually 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms and morepreferably 1 to 2 carbon atoms, and specifically includes a methylgroup, an ethyl group, an n-propyl group, an isopropyl group, an n-butylgroup, an isobutyl group, a sec-butyl group, a tert-butyl group, ann-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentylgroup, a neopentyl group, an n-hexyl group, an isohexyl group, asec-hexyl group, a tert-hexyl group, a cyclopropyl group, a cyclopentylgroup, a cyclohexyl group, etc.

Each of R⁷ and R⁸ in the general formula [3] is preferably a hydrogenatom.

An alkylene group represented by R⁹ may be straight chain, branched orcyclic and includes a group having usually 1 to 6 carbon atoms,preferably 1 to 4 carbon atoms and more preferably 1 to 2 carbon atoms,and specifically includes a methylene group, an ethylene group, atrimethylene group, a propylene group, a methylmethylene group, anmethylethylene group, an ethylmethylene group, a tetramethylene group, apentamethylene group, a hexamethylene group, a cyclopropylene group, acyclopentylene group, a cyclohexylene group, etc.

An arylene group represented by R⁹ includes usually a group having 6 to9 carbon atoms and specifically includes a p-phenylene group, ao-phenylene group, a m-phenylene group, a 2-methylphenylene group, a2,6-dimethylphenylene group, a 2,4-dimethylphenylene group, a2,3-dimethylphenylene group, etc.

An arylalkylene group represented by R⁹ includes usually a group having7 to 12 carbon atoms and specifically includes a phenylmethylene group,a phenylethylene group, a 1-phenylpropylene group, a 2-phenylpropylenegroup, a 1-phenylbutylene group, a 2-phenylbutylene group, anaphthylmethylene group, a naphthylethylene group, etc.

An arylenealkylene group represented by R⁹ includes a group havingusually 7 to 15 carbon atoms and preferably 7 to 10 carbon atoms, andspecifically, for example,

which are a combination of the above alkylene group and arylene group asappropriate.

R⁹ represented by the general formula [3] is preferably an arylene groupor an arylenealkylene group and particularly preferably anarylenealkylene group.

A ring that R² and R⁵ each may form together with carbon atoms of R³ orX, and carbon atoms of R⁶ or Y, respectively in the general formulas [1]and [2] includes usually a ring of 3 to 6 members and specifically acyclopropane ring, a cyclobutane ring, a cyclopentane ring, acyclohexane ring, and the like. A preferable glycidyl compoundrepresented by the general formula [1] or [2] includes specificallyglycidyl ethers such as vinylbenzyl glycidyl ether, vinylphenyl glycidylether, etc., glycidyl esters such as glycidyl benzoate, glycidylphenylacetate, etc.

A particularly preferable glycidyl compound relating to the presentinvention is a glycidyl ethers represented by the general formula [1].

An alkyl group represented by R¹⁰ and R¹¹ in the monomer represented bythe general formula [4] having a carboxyl group and a polymerizabledouble bond in the above (2), may be straight chain, branched or cyclicand includes a group having usually 1 to 6 carbon atoms, preferably 1 to4 carbon atoms and more preferably 1 to 2 carbon atoms, and specificallyincludes a methyl group, an ethyl group, an n-propyl group, an isopropylgroup, an n-butyl group, an isobutyl group, a sec-butyl group, atert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentylgroup, a tert-pentyl group, a neopentyl group, an n-hexyl group, anisohexyl group, a sec-hexyl group, a tert-hexyl group, a cyclopropylgroup, a cyclopentyl group, a cyclohexyl group, etc.

An aryl group represented by R¹¹ includes a group having usually 6 to 10carbon atoms and preferably 6 carbon atoms, and specifically, forexample, a phenyl group and a naphthyl group.

An aralkyl group represented by R¹¹ includes a group having usually 7 to12 carbon atoms and preferably 7 to 10 carbon atoms, and specifically, abenzyl group, a phenylethyl group, a phenylpropyl group, a phenylbutylgroup, a phenylpentyl group, a phenylhexyl group, etc.

An alkyl group which is used as a substituent that an aromatic ring inan aryl group and an aralkyl group represented by R¹¹ may have, may bestraight chain or branched, and includes usually a group having 1 to 4carbon atoms and specifically a methyl group, an ethyl group, ann-propyl group, an isopropyl group, an n-butyl group, an isobutyl group,a sec-butyl group, a tert-butyl group, etc., and an alkoxy group whichis used as a substituent that the above aromatic ring may have, may bestraight chain or branched, and includes usually a group having 1 to 4carbon atoms, and specifically a methoxy group, an ethoxy group, apropoxy group, an isopropoxy group, a butoxy group, an isobutoxy group,a sec-butoxy group, a tert-butoxy group, etc. A halogen atom that theabove aromatic ring may have, includes, for example, a chlorine atom, afluorine atom, a bromine atom and an iodine atom.

The above substituents of usually 1 to 5 and preferably 1 to 2 may bepresent in an aromatic ring in an aryl group and aralkyl group,represented by R¹¹.

An alkylene group, arylene group, arylalkylene group and arylenealkylenegroup represented by R¹² in the general formula [4], include similargroups as those represented by the above R⁹ in the general formula [3].

R¹² is preferably a direct-linkage in a monomer represented by thegeneral formula [4] and such a monomer is also called anacrylic-acid-based monomer in the present invention.

Among acrylic-acid-based monomers, acrylic acid and methacrylic acid aremore preferable examples, and methacrylic acid is particularlypreferable.

An alkyl group represented by R¹³ in the monomer represented by thegeneral formula [5] having a hydroxyl group in the above (3), an acyloxygroup, an isocyanato group or an amino group and a polymerizable doublebond, may be straight chain, branched or cyclic and includes a grouphaving usually 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms,more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbonatoms and particularly preferably 1 to 2 carbon atoms, and specificallyincludes a methyl group, an ethyl group, an n-propyl group, an isopropylgroup, an n-butyl group, an isobutyl group, a sec-butyl group, atert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentylgroup, a tert-pentyl group, a neopentyl group, an n-hexyl group, anisohexyl group, a sec-hexyl group, a tert-hexyl group, a 3-methylpentylgroup, a 2-methylpentyl group, a 1,2-dimethylbutyl group, an n-heptylgroup, an isoheptyl group, a sec-heptyl group, an n-octyl group, anisooctyl group, a sec-octyl group, an n-nonyl group, an n-decyl group,an n-undecyl group, an n-dodecyl group, an n-tridecyl group, ann-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, ann-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, ann-icosyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexylgroup, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, acyclodecyl group, a cycloundecyl group, a cyclododecyl group, acyclotridecyl group, a cyclotetradecyl group, a cyclopentadecyl group, acyclohexadecyl group, a cycloheptadecyl group, a cyclooctadecyl group, acyclononadecyl group, a cycloicosyl group, etc.

A hydroxyalkyl group represented by R¹⁴ that may have a carbonyl groupand/or an oxygen atom may be straight chain, branched or cyclic andincludes a group having usually 1 to 50 carbon atoms, preferably 2 to 20carbon atoms, more preferably 5 to 15 carbon atoms and still morepreferably 8 to 13 carbon atoms, and specifically includes ahydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a1-hydroxy-n-propyl group, a 2-hydroxy-n-propyl group, a3-hydroxy-n-propyl group, a 2-hydroxy-1-methylethyl group, a1-hydroxy-1-methylethyl group, a 1-hydroxy-n-butyl group, a2-hydroxy-n-butyl group, a 3-hydroxy-n-butyl group, a 4-hydroxy-n-butylgroup, a 3-hydroxy-2-methylpropyl group, a 2-hydroxy-2-methylpropylgroup, a 1-hydroxy-2-methylpropyl group, a 3-hydroxy-1-methylpropylgroup, a 2-hydroxy-1-methylpropyl group, a 1-hydroxy-1-methylpropylgroup, a 1-hydroxypentyl group, a 2-hydroxypentyl group, a3-hydroxypentyl group, a 4-hydroxypentyl group, a 5-hydroxypentyl group,a 4-hydroxy-1-methylbutyl group, a 3-hydroxy-1-ethylpropyl group, a1-hydroxy-1-ethylpropyl group, a 1-hydroxy-n-hexyl group, a3-hydroxy-n-hexyl group, a 6-hydroxy-n-hexyl group, a 5-hydroxy-3-pentylgroup, a 4-hydroxy-1,1-dimethylbutyl group, a 1-hydroxyheptyl group, a7-hydroxyheptyl group, a 8-hydroxyoctyl group, a 9-hydroxynonyl group, a10-hydroxydecyl group, a 11-hydroxyundecyl group, a 12-hydroxydodecylgroup, a 13-hydroxytridecyl group, a 14-hydroxytetradecyl group, a15-hydroxypentadecyl group, a 16-hydroxyhexadecyl group, a17-hydroxyheptadecyl group, a 18-hydroxyoctadecyl group, a19-hydroxynonadecyl group, a 20-hydroxyicosyl group, a25-hydroxypentacosyl group, a 30-hydroxytriacontyl group, a40-hydroxytetracontyl group, a 50-hydroxypentacontyl group, a1-hydroxycyclopropyl group, a 2-hydroxycyclopropyl group, a1-hydroxycyclopentyl group, a 2-hydroxycyclopentyl group, a3-hydroxycyclopentyl group, a 1-hydroxycyclohexyl group, a2-hydroxycyclohexyl group, a 3-hydroxycyclohexyl group, a1-hydroxycycloheptyl group, a 2-hydroxycyclooctyl group, a3-hydroxycyclononyl group, a 3-hydroxycyclodecyl group, a4-hydroxycyclopentadecyl group, etc.

The above hydroxyalkyl group may have carbonyl groups of usually 1 to 5,preferably 1 to 2 and more preferably 1 in its chain or at the end ofits chain, and/or oxygen atoms of usually 1 to 15, preferably 1 to 10and more preferably 3 to 5 in its chain or at the end of its chain.

A hydroxyalkyl group represented by R¹⁴ having a carbonyl group and/oran oxygen atom includes specifically, for example,

(wherein n is an integer of 1 to 6.)

(wherein m is an integer of 1 to 15.)

(wherein n is the same as the above.)and among these, a hydroxyalkyl group having only oxygen atoms ispreferable.

A hydroxyaryl group represented by R¹⁴ includes a group having usually 6to 10 carbon atoms and preferably 6 carbon atoms, and specifically, forexample, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group and a4-hydroxyphenyl group.

A hydroxyaralkyl group represented by R¹⁴ that may have a carbonyl groupand/or an oxygen atom may be straight chain, branched or cyclic andincludes a group having usually 7 to 50 carbon atoms, preferably 7 to 30carbon atoms and more preferably 8 to 20 carbon atoms, and specificallyincludes a 2-hydroxyphenylmethyl group, a 3-hydroxyphenylmethyl group, a4-hydroxyphenylmethyl group, a hydroxyphenylethyl group, ahydroxyphenylpropyl group, a hydroxyphenylbutyl group, ahydroxyphenylhexyl group, a hydroxyphenyheptyl group, ahydroxyphenyloctyl group, a hydroxyphenylnonyl group, ahydroxyphenyldecyl group, a hydroxyphenylundecyl group, ahydroxyphenyldodecyl group, a hydroxyphenyltridecyl group, ahydroxyphenyltetradecyl group, etc.

The above hydroxyaralkyl group may have carbonyl groups of usually 1 to5, preferably 1 to 2 and more preferably 1 in its chain or at the end ofits chain, and/or oxygen atoms of usually 1 to 15, preferably 1 to 10and more preferably 3 to 5 in its chain or at the end of its chain.

A preferable hydroxyaralkyl group represented by R¹⁴ having a carbonylgroup and/or an oxygen atom includes specifically, for example,

(wherein n is the same as the above.)

(wherein n is the same as the above.)

A hydroxyalkylaryl group represented by R¹⁴ that may have a carbonylgroup and/or an oxygen atom is straight chain, branched or cyclic andincludes a group having usually 7 to 50 carbon atoms, preferably 7 to 30carbon atoms and more preferably 8 to 20 carbon atoms, and specificallyincludes a 2-hydroxymethylphenyl group, a 3-hydroxymethylphenyl group, a4-hydroxymethylphenyl group, a hydroxyethylphenyl group, ahydroxypropylphenyl group, a hydroxybutylphenyl group, ahydroxyl-tert-butylphenyl group, a hydroxypentylphenyl group, ahydroxyisopentylphenyl group, a hydroxyhexylphenyl group, ahydroxyheptylphenyl group, a hydroxyoctylphenyl group, ahydroxynonylphenyl group, a hydroxydecylphenyl group, ahydroxyundecylphenyl group, a hydroxydodecylphenyl group, ahydroxytridecylphenyl group, a hydroxytetradecylphenyl group, etc.

The above hydroxyalkylaryl group may have carbonyl groups of usually 1to 5, preferably 1 to 2 and more preferably 1 in its chain or at an endof its chain, and/or oxygen atoms of usually 1 to 15, preferably 1 to 10and more preferably 3 to 5 in its chain or at an end of its chain.

A preferable hydroxyaralkyl group represented by R¹⁴ having a carbonylgroup and/or an oxygen atom includes specifically, for example,

(wherein n is the same as the above.)

(wherein n is the same as the above.)

An acyloxy group represented by R¹⁴ may be straight chain, branched orcyclic and includes a group having usually 2 to 6 carbon atoms andpreferably 2 to 4 carbon atoms, and specifically an acetyloxy group, apropionyloxy group, a butyryloxy group, a valeryloxy group, ahexanoyloxy group, etc.

An arylacyloxy group represented by R¹⁴ includes a group having usually7 to 15 carbon atoms and preferably 7 to 10 carbon atoms, andspecifically, for example, a benzoyloxy group and a naphthoyloxy group.

An isocyanatoalkyl group represented by R¹⁴ maybe straight chain,branched or cyclic and includes a group having usually 2 to 7 carbonatoms and preferably 2 to 5 carbon atoms, and specifically includes a2-isocyanatomethylphenyl group, a 3-isocyanatomethylphenyl group, a4-isocyanatomethylphenyl group, an isocyanatoethylphenyl group, anisocyanatopropylphenyl group, an isocyanatobutylphenyl group, anisocyanato-tert-butylphenyl group, an isocyanatopentylphenyl group, anisocyanatoisopentylphenyl group, an isocyanatohexylphenyl group, anisocyanatoheptylphenyl group, an isocyanatooctylphenyl group, anisocyanatononylphenyl group, an isocyanatodecylphenyl group, anisocyanatoundecylphenyl group, an isocyanatododecylphenyl group, anisocyanatotridecylphenyl group, an isocyanatotetradecylphenyl group,etc.

An isocyanatoaryl group represented by R¹⁴ includes a group havingusually 7 to 20 carbon atoms and preferably 7 to 15 carbon atoms, andspecifically, for example, an isocyanatophenyl group, anisocyanatonaphthyl group and an isocyanatoanthryl group.

An isocyanatoaralkyl group represented by R¹⁴ may be straight chain,branched or cyclic and includes a group having usually 8 to 20 carbonatoms and preferably 8 to 15 carbon atoms, and specifically includes a2-isocyahatophenylmethyl group, a 3-isocyanatophenylmethyl group, a4-isocyanatophenylmethyl group, an isocyanatophenylethyl group, anisocyanatophenylpropyl group, an isocyanatophenylbutyl group, anisocyanatophenylhexyl group, an isocyanatophenylheptyl group, anisocyanatophenyloctyl group, an isocyanatophenylnonyl group, anisocyanatophenyldecyl group, an isocyanatophenylundecyl group, anisocyanatophenyldodecyl group, an isocyanatophenyltridecyl group, anisocyanatophenyltetradecyl group, etc.

An isocyanatoalkylaryl group represented by R¹⁴ may be straight chain,branched or cyclic and includes a group having usually 8 to 20 carbonatoms and preferably 8 to 15 carbon atoms, and specifically includes a2-isocyanatomethylphenyl group, a 3-isocyanatomethylphenyl group, a4-isocyanatomethylphenyl group, an isocyanatoethylphenyl group, anisocyanatopropylphenyl group, an isocyanatobutylphenyl group, anisocyanato-tert-butylphenyl group, an isocyanatopentylphenyl group, anisocyanatoisopentylphenyl group, an isocyanatohexylphenyl group, anisocyanatoheptylphenyl group, an isocyanatooctylphenyl group, anisocyanatononylphenyl group, an isocyanatodecylphenyl group, anisocyanatoundecylphenyl group, an isocyanatododecylphenyl group, anisocyanatotridecylphenyl group, an isocyanatotetradecylphenyl group,etc.

An aminoalkyl group represented by R¹⁴ may be straight chain, branchedor cyclic and includes a group having usually 2 to 7 carbon atoms andpreferably 2 to 5 carbon atoms, and specifically includes a2-aminomethylphenyl group, a 3-aminomethylphenyl group, a4-aminomethylphenyl group, an aminoethylphenyl group, anaminopropylphenyl group, an aminobutylphenyl group, anamino-tert-butylphenyl group, an aminopentylphenyl group, anaminoisopentylphenyl group, an aminohexylphenyl group, anaminoheptylphenyl group, an aminooctylphenyl group, an aminononylphenylgroup, an aminodecylphenyl group, an aminoundecylphenyl group, anaminododecylphenyl group, an aminotridecylphenyl group, anaminotetradecylphenyl group, etc.

An aminoaryl group represented by R¹⁴ includes a group having usually 7to 20 carbon atoms and preferably 7 to 15 carbon atoms, andspecifically, for example, an aminophenyl group, an aminonaphthyl groupand an aminoanthryl group.

An aminoaralkyl group represented by R¹⁴ may be straight chain, branchedor cyclic and includes a group having usually 8 to 20 carbon atoms andpreferably 8 to 15 carbon atoms, and specifically a 2-aminophenylmethylgroup, a 3-aminophenylmethyl group, a 4-aminophenylmethyl group, anaminophenylethyl group, an aminophenylpropyl group, an aminophenylbutylgroup, an aminophenylhexyl group, an aminophenylheptyl group, anaminophenyloctyl group, an aminophenylnonyl group, an aminophenyldecylgroup, an aminophenylundecyl group, an aminophenyldodecyl group, anaminophenyltridecyl group, an aminophenyltetradecyl group, etc.

An aminoalkylaryl group represented by R¹⁴ may be straight chain,branched or cyclic and includes a group having usually 8 to 20 carbonatoms and preferably 8 to 15 carbon atoms, and specifically a2-aminomethylphenyl group, a 3-aminomethylphenyl group, a4-aminomethylphenyl group, an aminoethylphenyl group, anaminopropylphenyl group, an aminobutylphenyl group, anamino-tert-butylphenyl group, an aminopentylphenyl group, anaminoisopentylphenyl group, an aminohexylphenyl group, anaminoheptylphenyl group, an aminooctylphenyl group, an aminononylphenylgroup, an aminodecylphenyl group, an aminoundecylphenyl group, anaminododecylphenyl group, an aminotridecylphenyl group, anaminotetradecylphenyl group, etc.

In the above hydroxyaryl group, hydroxyaralkyl group, hydroxyalkylarylgroup, arylacyloxy group, isocyanatoaryl group, isocyanatoaralkyl group,isocyanatoalkylaryl group, aminoaryl group, aminoaralkyl group,aminoalkylaryl group, etc., an alkyl group which is used as asubstituent that an aromatic ring may have, may be straight chain orbranched, and includes usually a group having 1 to 4 carbon atoms andspecifically a methyl group, an ethyl group, an n-propyl group, anisopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group,a tert-butyl group, etc., and an alkoxy group which is used as asubstituent that the aromatic ring may have, may be straight chain orbranched, and includes usually a group having 1 to 4 carbon atoms andspecifically a methoxy group, an ethoxy group, a propoxy group, anisopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxygroup, a tert-butoxy group, etc. A halogen atom which is used as asubstituent that an aromatic ring may have, includes, for example, achlorine atom, a fluorine atom, a bromine atom and an iodine atom.

The above substituents of usually 1 to 5 and preferably 1 to 2 may bepresent in an aromatic ring in a hydroxyaryl group, a hydroxyaralkylgroup, a hydroxyalkylaryl group, an arylacyloxy group, an isocyanatoarylgroup, an isocyanatoaralkyl group, an isocyanatoalkylaryl group, anaminoaryl group, an aminoaralkyl group, an aminoalkylaryl group, etc.,represented by R¹⁴.

In a monomer represented by the general formula [5], R¹⁴ representspreferably a hydroxyalkyl group that may have a carbonyl group and/or anoxygen atom and more preferably a straight chain hydroxyalkyl group thatmay have an oxygen atom. R¹⁴, which is a group having an oxygen atom,has oxygen atoms of usually 1 to 15, preferably 1 to 10 and morepreferably 3 to 5 in the alkyl chain thereof.

An alkyl group represented by R¹⁵ in the general formula [5] may bestraight chain, branched or cyclic and includes a group having usually 1to 6 carbon atoms, preferably 1 to 4 carbon atoms and more preferably 1to 2 carbon atoms, and specifically includes a methyl group, an ethylgroup, an n-propyl group, an isopropyl group, an n-butyl group, anisobutyl group, a sec-butyl group, a tert-butyl group, an n-pentylgroup, an isopentyl group, a sec-pentyl group, a tert-pentyl group, aneopentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group,a tert-hexyl group, a cyclopropyl group, a cyclopentyl group, acyclohexyl group, etc.

An aryl group represented by R ¹⁵includes a group having usually 6 to 10carbon atoms and preferably 6 carbon atoms, and specifically, forexample, a phenyl group and a naphthyl group.

An aralkyl group represented by R¹⁵ may be straight chain, branched orcyclic and includes a group having usually 7 to 12 carbon atoms andpreferably 7 to 10 carbon atoms, and specifically a benzyl group, aphenylethyl group, a phenylpropyl group, a phenylbutyl group, aphenylpentyl group, a phenylhexyl group, etc.

A preferable monomer represented by the general formula [5] includesspecifically, for example,

Among these,

are particularly preferable.

2) A monomer having a polymerizable double bond, which is a raw materialfor synthesizing a straight chain organic polymer compound which is acopolymer before crosslinking to a crosslinked organic polymer compoundrelating to the present invention includes, for example, a monomerrepresented by the following general formula [6]:

(wherein R¹⁶ and R¹⁷ each independently represents a hydrogen atom or analkyl group having 1 to 6 carbon atoms; R¹⁹ represents a hydrogen atom,a halogen atom or an alkyl group having 1 to 6 carbon atoms; R¹⁸represents a carboxyl group, a hydroxyl group, an acyloxy group having 2to 6 carbon atoms, an arylacyloxy group having 7 to 15 carbon atoms, analkoxycarbonyl group having 2 to 6 carbon atoms, an alkyl group having 1to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms and anaralkyl group having 7 to 12 carbon atoms; an aromatic ring in the abovearylacyloxy group, aryl group and aralkyl group may have further analkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4carbon atoms or a halogen atom, as a substituent).

An alkyl group represented by R¹⁶ to R¹⁹ in the general formula [6] maybe straight chain, branched or cyclic and includes a group havingusually 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms and morepreferably 1 to 2 carbon atoms, and specifically includes a methylgroup, an ethyl group, an n-propyl group, an isopropyl group, an n-butylgroup, an isobutyl group, a sec-butyl group, a tert-butyl group, ann-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentylgroup, a neopentyl group, an n-hexyl group, an isohexyl group, asec-hexyl group, a tert-hexyl group, a cyclopropyl group, a cyclopentylgroup, a cyclohexyl group, etc.

A halogen atom represented by R¹⁹ includes, for example, a chlorineatom, a fluorine atom, a bromine atom and an iodine atom.

An acyloxy group represented by R¹⁸ may be straight chain, branched orcyclic and includes a group having usually 2 to 6 carbon atoms andpreferably 2 to 4 carbon atoms, and specifically includes an acetyloxygroup, a propionyloxy group, a butyryloxy group, an isobutyryloxy group,a valeryloxy group, an isovaleryloxy group, a pivaloyloxy group, etc.

An arylacyloxy group represented by R¹⁸ includes a group having usually7 to 15 carbon atoms and preferably 7 to 10 carbon atoms, andspecifically, for example, a benzoyloxy group and a naphthoyloxy group,etc.

An alkoxycarbonyl group represented by R¹⁸ may be straight chain,branched or cyclic and includes a group having usually 2 to 6 carbonatoms and preferably 2 to 4 carbon atoms, and specifically includes amethoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group,an isopropoxycarbonyl group, a butoxycarbonyl group, anisobutyloxycarbonyl group, a sec-butyloxycarbonyl group, atert-butyloxycarbonyl group, a pentyloxycarbonyl group, anisopentyloxycarbonyl group, a sec-pentyloxycarbonyl group, atert-pentyloxycarbonyl group, a cyclopropyloxycarbonyl group, acyclopentyloxycarbonyl group, etc.

An aryl group represented by R¹⁸ includes a group having usually 6 to 10carbon atoms and preferably 6 carbon atoms, and specifically, forexample, a phenyl group and a naphthyl group.

An aralkyl group represented by R¹⁸ may be straight chain, branched orcyclic and includes a group having usually 7 to 12 carbon atoms andpreferably 7 to 10 carbon atoms, and specifically a benzyl group, aphenylethyl group, a phenylpropyl group, a phenylbutyl group, aphenylpentyl group, a phenylhexyl group, etc.

An alkyl group which is used as a substituent that an aromatic ring inthe above arylacyloxy group, aryl group and aralkyl group represented byR¹⁸ may have, may be straight chain or branched and includes usually agroup having 1 to 4 carbon atoms, and specifically a methyl group, anethyl group, an n-propyl group, an isopropyl group, an n-butyl group, anisobutyl group, a sec-butyl group, a tert-butyl group, etc. An alkoxygroup, which is used as a substituent that an aromatic ring in the above3 groups may have, may be straight chain or branched and includesusually a group having 1 to 4 carbon atoms, and specifically a methoxygroup, an ethoxy group, a propoxy group, an isopropoxy group, a butoxygroup, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, etc.A halogen atom which is used as a substituent that an aromatic ring inthe above 3 groups may have, includes, for example, a chlorine atom, afluorine atom, a bromine atom and an iodine atom.

The above substituents of usually 1 to 5 and preferably 1 to 2 may bepresent in an aromatic ring in the hydroxyaryl group, hydroxyaralkylgroup and hydroxylalkylaryl group represented by R¹⁸.

R¹⁸ in a monomer represented by the general formula [6] is preferably anaryl group and more preferably a phenyl group, and such a monomer isalso called a styrene-based monomer in the present invention.

A preferable styrene-based monomer includes specifically styrene,α-methylstyrene, β-methylstyrene, α-ethylstyrene, o-methylstyrene,m-methylstyrene, p-methylstyrene, etc., and among these, styrene andα-methylstyrene are more preferable and styrene is particularlypreferable.

At least one monomer among 1) the above monomers represented by thegeneral formulas [1], [2], [4] and [5], having a crosslinkablefunctional group and a polymerizable double bond and 2) the abovemonomers represented by the general formula [6], having a polymerizabledouble bond, preferably has an aromatic ring in the molecule thereof.Among them, more preferably, a monomer represented by the generalformula [6] has an aromatic ring therein and, further preferably, allmonomers have an aromatic ring.

A crosslinked organic polymer compound relating to the present inventionis preferably a compound obtained by crosslinking a copolymer of (1) aglycidyl compound having an epoxy group and a polymerizable double bond,(2) a styrene-based monomer and (3) an acrylic-acid-based monomer or amonomer having a hydroxyalkyl group containing one or more oxygen atomsand a polymerizable double bond. Among these monomers, (3) a monomerhaving a hydroxyalkyl group containing one or more oxygen atoms and apolymerizable double bond is more preferable. A compound is furtherpreferable that is obtained by crosslinking (1) a copolymer of aglycidyl compound having an aromatic ring, an epoxy group and apolymerizable double bond, (2) a styrene-based monomer and (3) a monomerhaving an aromatic ring, a hydroxyalkyl group containing one or moreoxygen atoms and a polymerizable double bond. That is, it is desirablefor each monomer unit to have an aromatic ring, and monomer units ofusually 50% or more, preferably 70% or more and more preferably 100%based on all monomer units may have an aromatic ring.

A polymer or a copolymer obtained by polymerizing or copolymerizing oneor more kinds of the above 1) monomers having a crosslinkable functionalgroup and a polymerizable double bond, or a copolymer obtained bycopolymerizing one or more kinds of 1) monomers having a crosslinkablefunctional group and a polymerizable double bond and one or more kindsof monomers 2) having a polymerizable double bond, is sometimesabbreviated as a straight chain organic polymer compound.

A straight chain organic polymer compound having a crosslinkablefunctional group may be obtained by a well known polymerization method,wherein various monomers described above are dissolved or suspended in aproper solvent, followed by the addition of a suitable polymerizationinitiator and reacting while stirring and heating.

For example, an objective straight chain organic polymer compound can beobtained by mixing various monomers described above in ratio describedabove, followed by dissolving the monomers in a proper solvent of 1 to10 times as much as the monomers' volume, such as toluene, 1,4-dioxane,tetrahydrofuran, isopropanol, methyl ethyl ketone, etc., reacting themonomers at 50 to 150° C. for 1 to 20 hours in nitrogen stream in thepresence of a polymerization initiator of 0.1 to 30% by weight based onthe monomers, such as azoisobutyronitrile,2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(2-methylpropionicacid methyl ester), 2,2′-azobis (2-methylbutyronitrile), benzoylperoxide, lauroyl peroxide, etc., and subjecting the reaction mixture tothe post process according to an ordinary method for obtaining apolymer.

Weight average molecular weight (Mw) of a straight chain organic polymercompound relating to the present invention is not especially limited aslong as the compound is soluble in a proper solvent, and is usually2,000 to 3,000,000 and preferably 10,000 to 100,000.

A monomer unit constituting the above straight chain organic polymercompound includes a monomer unit represented by the following generalformula [1′] that is derived from a monomer represented by the abovegeneral formula [1]:

(wherein R¹ to R³ and R⁷ to R⁹ are the same as the above), a monomerunit represented by the following general formula [2′] that is derivedfrom a monomer represented by the above general formula [2]:

(wherein R⁴ to R⁹ are the same as the above), a monomer unit representedby the following general formula [4′] that is derived from a monomerrepresented by the above general formula [4]:

(wherein R¹⁰ to R¹² are the same as the above), a monomer unitrepresented by the following general formula [5′] that is derived from amonomer represented by the above general formula [5]:

(wherein R¹³ to R¹⁵are the same as the above), and a monomer unitrepresented by the following general formula [6′] that is derived from amonomer represented by the above general formula [6]:

(wherein, R¹⁶ to R¹⁹ are the same as the above)

When a combination of various monomer units constituting a straightchain organic polymer compound relating to the present invention is, forexample, (1) a glycidyl compound having an epoxy group and apolymerizable double bond, (2) a styrene-based monomer and (3) anacrylic-acid-based monomer, a straight chain organic polymer compoundhaving the above ratio of the monomer units represented by the generalformula [1′] or [2′], and the general formula [4′] is synthesized, sincethe monomer units among the monomer units represented by the generalformula [1′] or [2′], general formula [6′] and general formula [4′] thatcorrespond to above monomers respectively, have a crosslinkablefunctional group. When the combination is (1) a glycidyl compound havingan epoxy group and a polymerizable double bond, (2) a styrene-basedmonomer and (3) a monomer having a hydroxyalkyl group containing one ormore oxygen atoms and a polymerizable double bond, a straight chainorganic polymer compound having the above ratio of monomer unitsrepresented by the general formula [1′] or [2′], and the general formula[5′] is similarly synthesized. Ratio of (1) a glycidyl compound havingan epoxy group and a polymerizable double bond, (2) a styrene-basedmonomer and (3) a monomer having a hydroxyalkyl group containing one ormore oxygen atoms and a polymerizable double bond is preferably(1):(2):(3)=3 to 12:78 to 92:5 to 10.

In a so-called crosslinked organic polymer compound relating to thepresent invention, obtained by crosslinking a copolymer composed frommonomer units represented by the above general formulas [1′], [2′],[4′], [5′] and/or [6′], a crosslinking section exists between analkylene chain derived from a polymerizable double bond and anotheralkylene chain derived from a polymerizable double bond, which arerepresented by the following structural formula existing in a monomerunit:.

Number of atoms in the shortest chain of the above crosslinking sectionin the present invention is usually one or more. The preferable lowerlimit thereof is, in order, 2, 3, 5, 8, 10, 11, 15, 18 and 19 (thelatter is more preferable), and the preferable upper limit thereof is inorder, 400, 200, 100, 80, 70, 60, 50, 45, 40, 35, 30 and 28 (the latteris more preferable).

The above number of atoms in the shortest chain of a crosslinkingsection is, for example, 9, as shown by numbering in structural formula,when the crosslinking section of a polymer compound has structurerepresented as follows:

A catalyst composition of the present invention, where a palladiumcatalyst is physically carried on the crosslinked organic polymercompound such as described above, can be manufactured by homogenizing,for example, a straight chain organic polymer compound having acrosslinkable functional group and a palladium catalyst in a solventdissolving said straight chain organic polymer compound, followed bydepositing a composition formed and subjecting the crosslinkablefunctional group in said deposit composition to condensation forcrosslinking reaction. Additionary, in the above manufacture, apalladium catalyst is not necessary to be dissolved in a solvent as longas it is uniformly suspended. It is also possible to prepare anobjective catalyst composition of the present invention even from suchcondition.

It has been found that a palladium catalyst carried on a catalystcomposition of the present invention is converted to Pd(0) itselfwithout any coordinated ligand, when Pd(0) coordinated by a ligand(hereinafter, sometimes abbreviated to coordinated Pd(0)) is used as apalladium catalyst, and also a combination of suitable crosslinkablefunctional groups is subjected to a crosslinking reaction so that numberof atoms in the shortest chain of the final crosslinking section may be10 to 35 and preferably 15 to 30. It has been believed that Pd(0) itselfis too extremely unstable to be taken out in stable state, however, acatalyst composition physically carrying Pd(0) itself can be easilyobtained (without, for example, reduction treatment) by carrying out amethod of the present invention, by combining a specific palladiumcatalyst (coordinated Pd(0)) and a straight chain organic polymercompound having the above mentioned specific crosslinkable functionalgroup. A preferable combination of crosslinkable functional groups to beused for the above purpose includes, for example, a combination of aglycidyl group having an epoxy group in a monomer represented by thegeneral formula [1] or [2] and a hydroxyalkyl group that may contain acarbonyl group or/and an oxygen atom, represented by R¹⁴ in a monomerrepresented by the general formula [5]. A ligand to be used for theabove purpose includes 1,5-cyclooctadiene (COD), dibenzylideneacetone(DBA), bipyridine (BPY), phenanthrbline (PHE), benzonitrile (PhCN),isocyanide (RNC), triethylarsine (As(Et₃)), organic phosphine ligandssuch as dimethylphenylphosphine (P(CH₃)₂Ph), diphenylphosphinoferrocene(dPPf), trimethylphosphine (P(CH₃)₃), triethylphosphine (P(Et)₃),tri-tert-butylphosphine (P(^(t)-Bu)₃), tricyclohexylphosphine (PCy₃),trimethoxyphosphine (P(OCH₃)₃), triethoxyphosphine (P(OEt)₃),tri-tert-butoxyphosphine (P(O^(t)-Bu)₃), triphenylphosphine (PPh₃),1,2-bis(diphenylphosphino) ethane (DPPE), triphenoxyphosphine (P(OPh)₃),etc., and among these, an organic phosphine ligand is preferable andtriphenylphosphine, tri-tert-butylphosphine, triethylphosphine,trimethylphosphine, and the like are particularly preferable, andtriphenylphosphine is more preferable among them. It is not clear whysuch phenomenon occurs, but it is considered that crosslinking the abovespecific crosslinkable functional group causes steric hindrance, leadingto elimination of a ligand from coordinated Pd(0).

A carried amount of a palladium catalyst is usually 0.00001 to 0.01 moland preferably 0.00005 to 0.005 mol based on 1 g of a crosslinkedpolymer compound, while an amount of a palladium metal carried on acrosslinked polymer compound is usually 0.00001 to 50% by weight,preferably 0.0001 to 30% by weight, more preferably 0.001 to 15% byweight and still more preferably 0.01 to 10% by weight based on acrosslinked polymer compound.

A solvent to dissolve a straight chain organic polymer compound havingthe above crosslinkable functional group includes ethers such astetrahydrofuran, etc.: hydrocarbons such as cyclohexane, n-hexane, etc.:halogenated hydrocarbons such as methylene chloride, etc.

Temperature on dissolving a straight chain organic polymer compoundhaving a crosslinkable functional group in the above solvent, is usually−78 to 200° C., preferably −20 to 100° C. and more preferably 0 to 50°C.

A palladium catalyst is physically carried on a straight chain organicpolymer compound having a crosslinkable functional group by homogenizingthe straight chain organic polymer compound having a crosslinkablefunctional group and the palladium catalyst in the above solvent.

The above physically carrying state is different from carrying byso-called chemical bond such as an ionic bond and a covalent bond, andis simple fixation (carrying), that is, state that a palladium catalystis sandwiched or enveloped by molecular chains of a straight chainorganic polymer compound.

A composition obtained by filtering a composition deposited in asolvent, in which a palladium catalyst is physically carried on astraight chain organic polymer compound having a crosslinkablefunctional group, is heated, for example, without using a solvent andthus various crosslinkable functional groups contained in the abovecomposition cause crosslinking reaction to form crosslinkages. Degree ofthe resultant crosslinkage is not especialy limited as long as it doesnot impair objective catalyst activity, and the crosslinked monomerunits are about 0.1 to 10%, preferably about 0.5 to 5% and morepreferably about 0.5 to 3% based on the total monomer units.

Exception of the above method by heating, a crosslinking reactionrelating to the present invention can be carried out according toconventionally known methods used for crosslinking a straight chainorganic polymer compound, such as a method to use a crosslinking agent,a method to use a condensing agent, a method to use aradical-polymerization catalyst such as a peroxide and an azo compound,a method to add an acid and then to heat, and a method to react bycombination of a dehydrocondensation agent such as carbodiimides and anappropriate crosslinking agent.

The state of physically carrying in the palladium catalyst is a networkstructure formed by closslinking the polymer as a carrier. The networkstructure gives stronger physical fixation (carrying) of a palladiumcatalyst than the above mentioned physical carrying of a metal catalystgiven by a straight chain polymer compound, resulting in less leaking ofa palladium catalyst.

Crosslinking temperature of a crosslinkable functional group by heatingis, usually at 50 to 300° C., preferably 70 to 200° C. and morepreferably 100 to 180° C.

Reaction period on thermal crosslinking is usually 0.1 to 100 hours,preferably 1 to 50 hours and more preferably 3 to 10 hours.

When crosslinking is carried out by a crosslinking agent, thecrosslinking agent for a polymer having an epoxy group as acrosslinkable functional group: polyamine compounds such ashexamethylenediamine, hexamethylenetetramine, etc.; polyol compoundssuch as ethylene glycol, propylene glycol, glycerine, etc.;polycarboxylic acids and their anhydrides such as malonic acid, succinicacid, glutaric acid, adipic acid, pimelic acid, maleic acid, fumaricacid, etc., the closslinking agent for a polymer having a carboxyl groupas a crosslinkable functional group: polyhydroxy compounds such asethylene glycol, glycerine, etc.; alkylene oxides such as ethyleneoxide, propylene oxide, etc., the closslinking agent for a polymerhaving a hydroxyl group and/or an acyloxy group as a crosslinkablefunctional group: polycarboxylic acids and their anhydrides such asmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,maleic acid, fumaric acid, etc.; alkylene oxides such as ethylene oxide,propylene oxide, etc.; polyamine compounds such as hexamethylenediamine,hexamethylenetetramine, etc., the closslinking agent for a polymerhaving monomer unites derived from a monomer having an isocyanato groupas a crosslinkable functional group: polyhydroxy compounds such aswater, ethylene glycol, glycerine, etc.; polycarboxylic acids and theiranhydrides such as malonic acid, succinic acid, glutaric acid, adipicacid, pimelic acid, maleic acid, fumaric acid, etc.; polyamine compoundssuch as hexamethylenediamine, hexamethylenetetramine, etc., and theclosslinking agent for a polymer with an amino group as a crosslinkablefunctional group: polycarboxylic acids and their anhydrides such asmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,maleic acid, fumaric acid, etc.; alkylene oxides such as ethylene oxide,propylene oxide, etc.

When crosslinking is carried out using a condensing agent, thecondensing agent includes, for example, a dehydrating agent belonging tocarbodiimides such as dicyclohexyl carbodiimide for a polymer having acarboxyl group as a crosslinkable functional group.

Structure type at crosslinked section formed by the above mentionedcrosslinking reactions include:

(wherein R represents the above R²or R⁵; and R′ represents the above R³or R⁶) formed by, for example, thermal crosslinking of two epoxy groupswhich are crosslinkable functional groups;

(wherein R represents the above R²or R⁵; and R′ represents the above R³or R⁶) formed by, for example, thermal crosslinking of an epoxy group,which is a condensed functional group, and a carboxyl group;

(wherein R represents the above R²or R⁵; and R′ represents the above R³or R⁶) formed by, for example, thermal crosslinking of an epoxy group,which is a condensed functional group, and a hydroxyl group;

(wherein R represents the above R²or R⁵; and R′ represents the above R³or R⁶) formed by, for example, thermal crosslinking of an epoxy group,which is a condensed functional group, and an amino group;

(wherein R represents the above R² or R⁵; R′ represents the above R³ orR⁶; and —NH-Q-NH— represents a group derived from a polyamine) formedby, for example, crosslinking of two epoxy groups, which are condensedfunctional groups, using an amino group of a polyamine crosslinkingagent;

(wherein R represents the above R² or R⁵; R′ represents the above R³ orR⁶; and —O-Q-O— represents a group derived from a diol) formed by, forexample, crosslinking of two epoxy groups, which are crosslinkablefunctional groups, using a polyol crosslinking agent;

(wherein R represents the above R² or R⁵; R′ represents the above R³ orR⁶; and —O—OC-Q-CO—O— represents a group derived from a polycarboxylicacid) formed by, for example, crosslinking of two epoxy groups, whichare crosslinkable functional groups, using a polycarboxylic acidcrosslinking agent;

(wherein —O-Q-O— represents a group derived from a polyhydroxyl compoundor an alkylene oxide) formed by, for example, crosslinking of twocarboxyl groups which are crosslinkable functional groups, using apolyhydroxy compound or an alkylene oxide crosslinking agent;

(wherein —HN-Q-NH— represents a group derived from a polyamine) formedby, for example, crosslinking of two carboxyl groups which arecrosslinkable functional groups using a polyamine compound crosslinkingagent;

(wherein —OOC-Q-COO— represents a group derived from a polycarboxylicacid ) formed by, for example, crosslinking of two hydroxyl groups whichare crosslinkable functional groups, using a polycarboxylic acidcrosslinking agent;

(wherein —O-Q-O— represents a group derived from an alkylene oxide)formed by, for example, crosslinking of two hydroxyl groups which arecrosslinkable functional groups using an alkylene oxide crosslinkingagent;

formed by, for example, crosslinking of two isocyanato groups which arecrosslinkable functional groups using water;

(wherein —O-Q-O— represents a group derived from a dihydroxycompound)formed by, for example, crosslinking of two isocyanato groups,which are crosslinkable functional groups, using a polyhydroxy compoundcrosslinking agent;

(wherein —O—CO-Q-OC—O— represents a group derived from a dicarboxylicacid) formed by, for example, crosslinking of two isocyanato groups,which are crosslinkable functional groups, using a polycarboxylic acidcrosslinking agent;

(wherein —HN-Q-NH— represents a group derived from a polyamine) formedby, for example, crosslinking of two isocyanato groups, which arecrosslinkable functional groups, using a polyamine crosslinking agent;

formed by, for example, crosslinking of an amino group and a carboxylgroup, which are crosslinkable functional groups, using a dehydratingagent; and

formed by, for example, crosslinking of a hydroxyl group and a carboxylgroup, which are crosslinkable functional groups, using a dehydratingagent.

A crosslinked organic polymer compound relating to the present inventionmay be prepared by using the second polymer compound having apolymerizable double bond as a polymer compound before crosslinking.Such a method includes, for example, carrying out a crosslinkingreaction induced by action of a catalyst, for example, a peroxide suchas benzoyl peroxide and an azo compound such as2,2′-azobisisobutyronitrile, in the presence or absence of a monomerhaving a polymerizable double bond such as maleic anhydride.

A reaction example for producing a crosslinked organic polymer compoundof the present invention is shown below, where raw material monomers ofvinylglycidyl ether, acrylic acid and styrene are polymerized to obtaina polymer compound before crosslinking, which is then crosslinked.

In thus obtained catalyst composition of the present invention, apalladium catalyst is physically carried on a crosslinked organicpolymer compound. Consequently, electrons are provided by an aromaticring in a crosslinked organic polymer compound carrier, in particular,an aromatic ring in a styrene-based monomer unit, which is considered toenhance catalytic activity compared with conventional palladiumcatalysts.

A catalyst composition of the present invention is very useful as acatalyst for various reactions, because of superior solvent resistance,little leak of a metal catalyst carried on a crosslinked organic polymercompound, no deterioration of catalyst activity even by repeated use andeasy handling. Further, a palladium catalyst of 0 valence, inparticular, Pd(0) not coordinated, which has not been easily handled,because it may sometimes spontaneously ignite in air or lower itsactivity in air, can be furnished with higher activity than conventionalones and can be used and stored safely for a long period, in accordancewith a catalyst composition of the present invention, where a palladiumcatalyst is physically carried on a crosslinked organic polymercompound.

Since having superior characteristics mentioned above, a catalystcomposition of the present invention can be advantageously used inindustry as a catalyst for various chemical reactions.

Hydrogenation (reduction) of a carbon-carbon double bond in a compoundhaving a reactive double bond is one example of these reactions. Thismeans the addition of hydrogen to a reactive carbon-carbon double bond,and for example, an olefin compound is added with hydrogen to get acarbon-carbon single bond, thus leading to easy reduction of the olefincompound, by using a catalyst composition of the present invention as acatalyst.

A compound having a reactive double bond as a reaction substrateincludes any compound as long as it has a reactive double bond, forexample, a polymer compound and a compound having any functional groupand/or aromatic ring as a substituent, as long as these compounds haveat least one reactive double bond in a molecule, to say nothing of anolefin compound, a diene compound and an unsaturated cyclic hydrocarboncompound.

Use amount of a catalyst composition of the present invention for ahydrogenation reaction is usually 0.000001 to 50% by weight, preferably0.00001 to 20% by weight and more preferably 0.001 to 10% by weightbased on a reaction substrate.

The above hydrogenation reaction may be carried out either in anappropriate solvent or in non-solvent.

A solvent may be any one as long as it is liquid at reactiontemperature, and includes specifically, aliphatic hydrocarbons such aspropane, butane, pentane, hexane, heptane, octane, nonane, decane,undeane, dodecane, tridecane, tetradecane, pentadecane, hexadecane,heptadecane, octadecane, nonadecane, icosane, cyclopropane, cyclobutane,cyclopentane, cyclohexane, cycloheptane, etc.; aromatic hydrocarbonssuch as benzene, naphthalene, etc.; alkyl group substituted aromatichydrocarbons such as toluene, xylene, mesitylene, ethylbenzene,propylbenzene, cumene, butylbenzene, isobutylbenzene, tert-butylbenzene,pentylbenzene, hexylbenzene, etc.; biphenyl derivatives such asbiphenyl, terphenyl, etc.; halogen substituted aromatic hydrocarbonssuch as fluorobenzene, difluorobenzene, trifluorobenzene,tetrafluorobenzene, pentafluorobenzene, hexafluorobenzene,chlorobenzene, dichlorobenzene, trichlorobenzene, tetrachlorobenzene,pentachlorobenzene, hexachlorobenzene, bromobenzene, dibromobenzene,tribromobenzene, tetrabromobenzene, pentabromobenzene, hexabromobenzene,iodobenzene, diiodobenzene, triiodobenzene, tetraiodobenzene,pentaiodobenzene, hexaiodobenzene, chloronaphthalene,dichloronaphthalene, fluorotoluene, chlorotoluene, bromotoluene,iodotoluene, etc.; alkoxy group substituted aromatic hydrocarbons suchas anisole, ethoxybenzene, propyloxybenzene, butoxybenzene,pentyloxybenzene, hexyloxybenzene, etc.; alcohols such as methanol,ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol,nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol,pentadecanol, hexadecanol, benzyl alcohol, etc.; phenol derivatives suchas phenol, catechol, resorcinol, cresol, etc.; aliphatic carboxylic acidesters such as methyl formate, ethyl formate, methyl acetate, ethylacetate, butyl acetate, methyl propionate, ethyl propionate, butylpropionate, ethyl butyrate, ethyl butyrate, ethyl valerate, ethylhexanoate, dimethyl oxalate, diethyl oxalate, dimethyl malonate, diethylmalonate, dibutyl malonate, dimethyl succinate, diethyl succinate,dimethyl adipate, diethyl pimelate, ethyl acetoacetate, etc.; aromaticcarboxylic acids such as methyl benzoate, ethyl benzoate, propylbenzoate, butyl benzoate, etc.; ketones such as acetone, methyl ethylketone, diethyl ketone, hexanone, cyclohexylacetone, acetophenone,propiophenone, acetoin, etc.; ethers such as dimethyl ether, methylethyl ether, diethyl ether, diisopropyl ether, tert-butyl methyl ether,tetrahydrofuran, tetrahydropyran, 1,4-dioxane, cyclopentyl phenyl ether,etc.; aldehydes such as formaldehyde, acetaldehyde, propionaldehyde,butylaldehyde, isobutylaldehyde, valeraldehyde, isovaleraldehyde,benzaldehyde, anisaldehyde, nicotinaldehyde, glyceraldehyde,glycolaldehyde, malonaldehyde, succinaldehyde, glutaraldehyde,adipinaldehyde, phthalaldehyde, isophthalaldehyde, terephthalaldehyde,glyoxal, aminoacetoaldehyde, aminobutylaldehyde, asparticlaldehyde,etc.; amines such as ammonia, methylamine, ethylamine, dimethylamine,trimethylamine, diethylamine, triethylamine, 1-ethylbutylamine,cyclohexylamine, naphthylamine, benzofuranamine, etc. These solvents areselected as appropriate depending on such as kind of a reactionsubstrate, reaction temperature or an objective reaction period, and maybe used either alone or in a proper combination of two or more solvents.

It is preferable to use a solvent not comprising a compound havingstructure to induce a hydrogenation reaction of a carbon-carbon doublebond thereof so as to give priority to a hydrogenation reaction of areaction substrate.

A reaction can be carried out in suspended state, even if a reactionsubstrate is not completely dissolved in the above solvent.

When a solvent is not used, a reaction substrate may be reacted inmolten state or in vapor phase.

Reaction temperature is usually −30 to 300° C., preferably 0 to 200° C.and more preferably 20 to 200° C.

Reaction period is usually 0.1 to 200 hours, preferably 0.2 to 24 hoursand more preferably 1 to 12 hours.

Reaction pressure is usually atmospheric pressure to 100 MPa, preferablyatmospheric pressure to 10 MPa and more preferably atmospheric pressureto 1 MPa.

With regard to reaction conditions other than the conditions describedabove, and a method for post processing, those in accordance with knownhydrogenation reactions may be adopted.

The above hydrogenation reaction, in which a catalyst composition of thepresent invention is used as a catalyst, is shown by the followingreaction scheme, taking benzalacetone as an example of olefin.

Metal catalysts of 0 valence such as platinum, palladium, ruthenium,iridium and Raney nickel have been used in a hydrogenation reaction ofan olefin, and the like as a heterogeneous catalyst, which is insolublein a reaction solvent. In this connection, platinum has been used inPtO₂ form and other metals have been used in carried state on an inertinorganic carrier such as activated carbon, alumina, barium sulfate andcalcium carbonate. Among these, palladium fixed on activated carbon(palladium-carbon) has been most frequently used for reduction(hydrogenation) of a carbon-carbon double bond using hydrogen.

However, palladium fixed on activated carbon has a problem wherein thefixed metal leaks during use and cannot be reused.

The above catalyst composition of the present invention has equivalentor higher activity than a conventional palladium-carbon catalysts andeasily handled, and also keeps its activity in repeated use of manytimes with little metal leakage, and therefore is very useful as acatalyst for the above hydrogenation reaction of an olefin, and thelike.

A catalyst composition of the present invention is also useful forreduction of a carbonyl group, a halogen, a nitro group, a nitrilegroup, and the like, in addition to hydrogenation of an olefin, etc.

A catalyst composition of the present invention is also useful as acatalyst for so-called substitution reaction at an allyl position.

An allyl carbonate and a carbon nucleophilic agent are dissolved in aproper solvent and a proper ligand (for example, triphenylphosphine) isadded thereto and then the obtained solution is subjected to a reactionunder stirring in the presence of a catalyst composition of the presentinvention, to obtain a compound where the carbon nucleophilic agentsubstitutes at carboxyl ester position of an allyl carbonate.

A substitution reaction at the above allyl position, where allyl methylcarbonate is used as an allyl carbonate and phenyl dimethyl malonate isused as a carbon nucleophilic agent are used, is shown by reactionscheme below.

A catalyst composition of the present invention to be used in asubstitution reaction at the above allyl position preferably comprises acrosslinked organic polymer compound not having an ester linkage.

An allyl carbonate in reaction substrates in a substitution reaction atthe allyl position of the present invention includes, allyl methylcarbonate, allyl ethyl carbonate, allyl propyl carbonate, allyl phenylcarbonate, etc.

A carbon nucleophilic agent includes a compound of low electron-densitysuch as methylene chloride, malonic acid ester, cyanoacetic acid ester,activated carbon, etc.

A ligand to be added on a reaction includes, organic phosphine ligandssuch as triphenylphosphine, tri-tert-butylphosphine, triethylphosphine,trimethylphosphine, and the like and among these, triphenylphosphine ispreferable.

A reactive solvent is not especially limited as long as the solvent canbe used in this field.

Reaction temperature is usually −78 to 200° C., preferably −20 to 100°C. and more preferably 0 to 50° C.

Reaction period is usually 0.1 to 200 hours, preferably 0.2 to 24 hoursand more preferably 1 to 12 hours.

A reaction similar to the above reaction can be carried out in highyield, by using a catalyst composition of the present invention as acatalyst, wherein a crosslinked organic polymer compound has an aromaticring such as a styrene monomer unit, and also using an oxygennucleophilic agent such as phenol having an electron acceptor group suchas a phenol group, and further a nitro group and a cyano group, insteadof the above carbon nucleophilic agent.

It has been known that reactivity of a reaction using an oxygennucleophilic agent, such as phenol having an electron acceptor group, isremarkably lowered compared with that of the above substitution reactionat the allyl position using a carbon nucleophilic agent. Therefore, itis estimated that in the above catalyst composition of the presentinvention, an electron is donated to a carried metal catalyst by anaromatic ring of a styrene monomer unit existing in the carrier part ofthe catalyst composition, that is, a crosslinked organic polymercompound, leading to improved activity of the catalyst itself.

A catalyst composition of the present invention is also useful as anoxidation catalyst of alcohols.

For example, in oxidation of secondary alcohols and allyl-type alcohols,such alcohols react first with allyl carbonate to form an allylcarbonate (that is, diester), which are reacted in a proper solvent inthe presence of a catalyst composition of the present invention, toinduce beta elimination to form a ketone, as a result, the secondaryalcohol and the allyl-type alcohol are oxidated.

An allyl-type alcohol in the above oxidation of alcohols includes, allylalcohol, crotyl alcohol, cinnamyl alcohol, etc.

A primary alcohol such as cinnamyl alcohol can be oxidized using acatalyst composition of the present invention as a catalyst in a“one-pot reaction” as shown by reaction scheme below.

As described above, when triphenylphosphine is present in a system of areaction using an allyl carbonate, a substitution reaction at the allylposition proceeds, while an oxidation reaction does not. From the factthat in the above oxidation reaction of cinnamyl alcohol, nosubstitution reaction at the allyl position occurs even by using acatalyst composition of the present invention, while objective oxidationof the alcohol proceeds, it can be confirmed that no phosphine ligand iscontained in a catalyst composition of the present invention, although acatalyst composition of the present invention is produced from a metalcatalyst coordinated with a phosphine ligand as a raw material.

As described above, a catalyst composition of the present invention,where a palladium catalyst is physically carried on a crosslinkedorganic polymer compound, obtained by homogenizing a straight chainorganic polymer compound having a crosslinkable functional group and thepalladium catalyst in a solvent dissolving these, followed by depositinga composition formed and subjecting the crosslinkable functional groupin said deposit composition to condensation for crosslinking reaction,can be handled safely and easily without danger of spontaneous ignitionand is very useful as a catalyst for various reactions and also hasadvantage that it keeps its activity even in repeated use and a metalcatalyst does not leak from its polymer compound carrier. It has beensaid that a heterogeneous catalyst such as a catalyst composition of thepresent invention generally has lower activity, however, a catalystcomposition of the present invention has surprising effect of ratherhigher catalyst activity than a conventional catalyst.

The present invention will be described hereinbelow in more detail withExamples and Comparative Examples, which do not constitute limitingaspects of the present invention.

EXAMPLE Referential Example 1 Synthesis of a Glycidyl Compound

After washing 4.00 g of sodium hydride (purity: 60%) with petroleumether, it was dried under reduced pressure, and 200 ml ofdimethylformamide was added thereto, and cooled in an ice bath. Then,6.6 ml of glycidol was added to the system while stirring, and thereaction solution was reacted while stirring at room temperature for onehour. After completing the reaction, 7 ml of 4-vinylbenzyl chloride and1.84 g of tetran n-butylammonium iodide were added to the reactionsolution while stirring for 5 hours. After completing the reaction, thereaction solution was ice-cooled, and diluted with diethyl ether andthen the reaction was terminated by adding a saturated aqueous solutionof ammonium chloride. After separating an organic layer of the solution,a water layer was extracted with diethyl ether and it was combined withthe organic layer separated, washed with a saturated aqueous solution ofsodium bicarbonate and saturated salt water, and dried with sodiumsulfate anhydride. After drying, this was filtrated, condensed underreduced pressure and purified by silica gel column chromatography toobtain 6.86 g of 4-vinylbenzyl glycidyl ether (yield: 73%). Measurementresults by ¹H-NMR and ¹³C-NMR of 4-vinylbenzyl glycidyl ether obtainedare shown below.

¹H-NMR (CDCl₃) δ=2.60 (d, 1H, J=2.5, 5.1 Hz), 2.57 (d, 1H, J=4.2, 5.1Hz), 3.17 (dddd, 1H, J=2.7, 2.9, 5.1, 5.7 Hz), 3.41 (dd, 1H, J=5.7, 11.3Hz), 3.75 (dd, 1H, J=2.9, 11.3 Hz), 4.56 (dd, 2H, J=12.1, 22.8 Hz), 5.23(d, 1H, J=11.0 Hz), 5.74 (d, 1H, J=17.6 Hz), 6.70 (dd, 1H, J=11.0, 17.6Hz), 7.30 (d, 1H, J=8.3 Hz), 7.38 (d, 1H, J=8.3 Hz) ¹³C-NMR (CDCl₃)δ=40.2, 50.7, 70.7, 72.9, 113.8, 126.2, 127.9, 136.4, 137.0, 137.4

Referential Example 2 Synthesis of a Monomer Containing a HydroxyalkylGroup Having an Oxygen Atom and a Polymerizable Double Bond

To 200 ml of methylene chloride, 7.0 ml of triethylamine and 9.71 g oftetraethylene glycol were added, and then they were cooled to 0° C., and4.9 ml of methacryloyl chloride was added thereto. After the reactionmixture was reacted while stirring at room temperature for 12 hours, asolvent was distilled off under reduced pressure, and by adding diethylether to the residue, a hydrochloric acid salt of triethylamine wasseparated by filtration. The filtrate was condensed again under reducedpressure, and after methylene chloride was added to the residue and theywere washed with water and saturated salt water, it was dried withsodium sulfate anhydride, followed by drying the solution, filtrationand condensation under reduced pressure to obtain 10.3 g of a product(yield: 78%). According to the measurement results by ¹H-NMR, it wasaffirmed that said product is tetraethylene glycol monomethacryloylester.

Referential Example 3 Synthesis of a Monomer Containing a HydroxyalkylGroup Having an Oxygen Atom and a Polymerizable Double Bond (1)Synthesis of 3-hydroxy-2-phenylpropene

A 12.5 ml of decane solution of 5 to 6 mol/L of per-tert-butylalcohol isdiluted with 50 ml of methylene chloride, then 111 mg of seleniumdioxide and 90.1 mg of an acetic acid were added thereto to react whilestirring at room temperature for 30 min. Then, 6.5 ml of 2-phenylpropenewas added to the reaction solution to react while stirring for 72 hours,followed by condensation under reduced pressure, and purification bysilica gel column chromatography to obtain 3.98 g of3-hydroxy-2-phenylpropene (yield: 59%). Measurement results by ¹H-NMRand ¹³C-NMR of 3-hydroxy-2-phenylpropene obtained are shown below.

¹H-NMR (CDCl₃) δ=1.27 (s, 1H), 4.55 (s, 2H), 5.36(s, 1H), 5.48 (s, 1H),7.28-7.40 (m, 3H), 7.42-7.50 (m, 2H)

¹³C-NMR (CDCl₃) δ=65.0, 112.6, 126.0, 127.9, 128.5, 138.4, 147.2

(2) Synthesis of 3-chloro-2-phenylpropene

To 3.94 g of 3-hydroxy-2-phenylpropene obtained, a 10 ml ofdimethylformamide solution containing 3.84 g of s-collidine and 1.245 gof lithium chloride was added, and they were cooled to 0° C. To asuspension obtained, 2.45 ml of methanesulfonyl chloride was added indrop-wise. After heating the reaction solution to room temperature over8 hours, it was diluted with diethyl ether and the reaction wasterminated by adding water. After separating an organic layer of thesolution, a water layer was extracted twice with diethyl ether, and thenit was combined with the organic layer separated, followed by washingwith water and saturated salt water, and drying with sodium sulfateanhydride. After drying, this was filtrated and condensed under reducedpressure, and purified by silica gel column chromatography to obtain3.53 g of 3-chloro-2-phenylpropene (yield: 79%). Measurement results by¹H-NMR and ¹³C-NMR of 3-chloro-2-phenylpropene obtained are shown below.

¹H-NMR (CDCl₃) δ=4.50 (s, 2H), 5.49(s, 1H), 5.60 (s, 1H), 7.30-7.60 (m,5H)

¹³C-NMR (CDCl₃) δ=46.5, 116.7, 126.1, 128.2, 128.5, 137.6, 143.9

(3) Synthesis of tetraethylene glycol mono-2-phenyl-2-propenyl ether

After 1.82 g of sodium hydride (purity: 60%) is washed with petroleumether, it was dried under reduced pressure, followed by the addition of70 ml of tetrahydrofuran thereto and cooling in an ice bath. Then, asolution dissolving 8.81 g of tetraethylene glycol was added to 10 ml oftetrahydrofuran in the system while stirring. After the reactionsolution was reacted while stirring at room temperature for one hour, asolution dissolving 3.46 g of 3-chloro-2-phenylpropene obtained above in10 ml of tetrahydrofuran was added in the system while stirring, andfurther they were reacted while stirring for 12 hours. After completingthe reaction, the reaction solution was ice-cooled, and was diluted withdiethyl ether and then the reaction was terminated by adding a saturatedaqueous solution of ammonium chloride. After separating an organic layerof the reaction solution, a water layer was extracted with diethyl etherand it was combined with the organic layer separated. And the solutionobtained was washed with a saturated aqueous solution of sodiumbicarbonate and saturated salt water, and dried with sodium sulfateanhydride. After drying, this was filtrated and then condensed underreduced pressure, and purified by silica gel column chromatography toobtain 4.52 g of tetraethylene glycol mono-2-phenyl-2-propenyl ether(yield: 64%). Measurement results by ¹H-NMR and ¹³C-NMR of tetraethyleneglycol mono-2-phenyl-2-propenyl ether obtained are shown below.

¹H-NMR (CDCl₃) δ=2.72 (s, 1H), 3.58-3.74 (m, 16H), 4.42 (s, 2H), 5.34(d, 1H, J=1.2 Hz), 5.53 (d, 1H, J=0.5 Hz), 7.25-7.36 (m, 3H), 7.44-7.52(m, 2H)

¹³C-NMR (CDCl₃) δ=61.7, 69.2, 70.3, 70.53, 70.58, 72.4, 73.1, 114.4,126.1, 127.7, 128.3, 138.7, 144.0

Referential Example 4 Synthesis of a straight Chain Polymer compound-1

To 50 ml of toluene, 37.4 g of styrene, 3.8 g of 4-vinylbenzyl glycidylether obtained in Referential Example 1, 1.7 g of a methacrylic acid and1 g of 2,2′-azobis(2,4-methylvaleronitrile) were added, and they werereacted by heating under refluxing at 70 to 80° C. for 8 hours. Aftercompleting the reaction, the reaction solution was cooled to roomtemperature, then dropped to 500 ml of ice-cooled hexane to solidify apolymer. The polymer solidified was filtered off, followed by dissolvingin 50 ml of THF, and pouring 500 ml of hexane to re-precipitate. Thisoperation was repeated, followed by drying under reduced pressure toobtain 11.8 g of a polymer (yield: 65%) . According to the measurementresults by ¹H-NMR, ratio (X:Y:Z) of each monomer unit of the polymerobtained (styrene/4-vinylbenzyl glycidyl ether/methacrylic acid) wasfound to be 61:28:11. Weight average molecular weight M_(w) of thepolymer obtained was 19,504.

Referential Example 5 Synthesis of a Straight Chain Polymer Compound-2

To 100 ml of chloroform, 23.3 g of styrene, 5.33 g of 4-vinylbenzylglycidyl ether obtained in Referential Example 1, 7.74 g oftetraethylene glycol monomethacryloyl ester obtained in ReferentialExample 2, and 328.4 mg of 2,2′-azobisisobutyronitrile were added, andthey were reacted by heating under refluxing at 80° C. for 48 hours.After completing the reaction, the reaction solution was cooled to roomtemperature, then dropped into 500 ml of ice-cooled methanol to solidifya polymer. The polymer solidified was filtered off, washed withmethanol, and then dried under reduced pressure to obtain 23.03 g of apolymer (yield: 65%). According to the measurement results by ¹H-NMR,ratio (X:Y:Z) of each monomer unit of the polymer obtained(styrene/4-vinylbenzyl glycidyl ether/tetraethylene glycolmonomethacryloyl ester) was found to be 82:10:8. Weight averagemolecular weight M_(w) of the polymer obtained was 22,087, numberaverage molecular weight M_(n) thereof was 12,473 and M_(w)/M_(n) was1.771.

Referential Example 6 Synthesis of a Straight Chain Polymer Compound-3

To 100 ml of chloroform, 23.3 g of styrene, 5.33 g of 4-vinylbenzylglycidyl ether obtained in Referential Example 1, 9.08 g oftetraethylene glycol mono-2-phenyl-2-propenyl ether obtained inReferential Example 3, and 328.4 mg of 2,2′-azobisisobutyronitrile wereadded, and they were reacted by heating under refluxing at 80° C. for 48hours. After completing the reaction, the reaction solution was cooledto room temperature, then dropped into 500 ml of ice-cooled methanol tosolidify a polymer. The polymer solidified was filtered off, washed withmethanol, and dried under reduced pressure to obtain 23.0 g of a polymer(yield: 68%). According to the measurement results by ¹H-NMR, ratio(X:Y:Z) of each monomer unit of the polymer obtained(styrene/4-vinylbenzyl glycidyl ether/tetraethylene glycolmono-2-phenyl-2-propenyl ether) was found to be 90:4:6. Weight averagemolecular weight M_(w) of the polymer obtained was 69,985, numberaverage molecular weight M_(n) thereof was 12,098 and M_(w)/M_(n) was5.785.

Example 1 Synthesis of a Catalyst Composition of the Present Invention(Carried on an MSV Polymer)

Into 20 ml of tetrahydrofuran, 1.0 g of a straight chain polymercompound obtained in Referential Example 4 was dissolved, and 200 mg oftetrakis (triphenylphosphine) palladium was added thereto, and they werereacted while stirring at room temperature for 24 hours. Aftercompleting the reaction, hexane, which is a poor solvent of the reactionsolution, was added thereto to solidify a polymer, and they were left tostand for 12 hours. After decantation of a hexane layer, the polymer wasdried under reduced pressure. After the polymer obtained was pulverized,it was agitated at 120° C. for 2 hours in non-solvent condition, and thepolymer was cooled to room temperature. Then, tetrahydrofuran was addedthereto and they were agitated, followed by filtering off, washing withtetrahydrofuran and drying under reduced pressure to obtain 750 mg of acatalyst composition of the present invention.

From the filtrate, whole amount of triphenylphosphine could be recoveredcorresponding to that of tetrakis(triphenylphosphine) palladium used.Introduction ratio of palladium metal on a polymer carrier was 93%, andpalladium metal contained in 1 g of a catalyst composition of thepresent invention was 0.215 mmol.

In this connection, introduction ratio of palladium metal was determinedby measuring residual palladium metal in filtrate using a fluorescentX-ray spectrometer, and by comparing with amount of metal used in areaction (the same hereinafter).

Example 2 Synthesis of a Catalyst Composition of the Present Invention

Into 20 ml of tetrahydrofuran, 1.0 g of a straight chain polymercompound obtained in Referential Example 6 was dissolved, and 100 mg oftetrakis (triphenylphosphine) palladium was added thereto, and they werereacted while stirring at room temperature for 24 hours. Aftercompleting the reaction, hexane, which is a poor solvent of the reactionsolution, was added thereto to solidify a polymer, and they were left tostand for 12 hours. After decantation of a hexane layer, the polymer wasdried under reduced pressure. After the polymer obtained was pulverized,it was agitated at 120° C. for 2 hours in non-solvent condition, andcooled to room temperature. Then, tetrahydrofuran was added thereto andthey were agitated, followed by filtering off, washing withtetrahydrofuran and drying under reduced pressure to obtain 750 mg of acatalyst composition of the present invention. From the filtrate, wholeamount of triphenylphosphine could be recovered corresponding to that oftetrakis(triphenylphosphine) palladium used. And introduction ratio ofpalladium metal on a polymer carrier was 97%, and palladium metalcontained in 1 g of a catalyst composition of the present invention was0.108 mmol.

Example 3 Synthesis of a Catalyst composition of the Present Invention

The same procedure as Example 2 was conducted except that a straightchain polymer compound obtained in Referential Example 5 was used as apolymer carrier instead of a straight chain polymer compound obtained inReferential Example 6, and 792 mg of a catalyst composition of thepresent invention was obtained. From the filtrate, whole amount oftriphenylphosphine was recovered corresponding to that oftetrakis(triphenylphosphine) palladium used. And introduction ratio ofpalladium metal on a polymer carrier was 97%, and palladium metalcontained in 1 g of a catalyst composition of the present invention was0.108 mmol.

Experimental Example 1 Hydrogenation Reaction of an Olefin-1

To 5 ml of tetrahydrofuran, 115 mg of a catalyst composition of thepresent invention (palladium metal content: 0.025 mmol) obtained inExample 1 and 73.0 mg of benzalacetone were added, and they were reactedwhile stirring under hydrogen atmosphere at room temperature for onehour. After completing the reaction, hexane was added to the reactionsolution and they were agitated. When the reaction solution becametransparent, the catalyst composition of the present invention used wasfiltrated. After a filtrate was condensed, it was purified by silica gelthin-layer chromatography to obtain 50.3 mg of 4-phenyl-2-butanone(yield: 68%). By measurement of the filtrate before purifying with afluorescent X-ray spectrometer, it was affirmed that palladium leakagewas not observed from a catalyst composition of the present invention.

And a catalyst composition of the present invention filtered off waswashed with tetrahydrofuran, and then recovered by drying under reducedpressure.

It was proved by the measurement results using ¹H-NMR and ¹³C-NMR that aproduct obtained is 4-phenyl-2-butanone.

Experimental Example 2 Hydrogenation Reaction of an Olefin-2

To 5 ml of tetrahydrofuran, 231 mg of a catalyst composition of thepresent invention (palladium metal content: 0.025 mmol) obtained inExample 2 and 73.0 mg of benzalacetone were added, and they were reactedwhile stirring under hydrogen atmosphere at room temperature for onehour. After completing the reaction, hexane was added to the reactionsolution, followed by stirring and filtering a catalyst composition ofthe present invention used, when the reaction solution becametransparent. After the filtrate was condensed, it was purified by silicagel thin-layer chromatography to obtain 60.0 mg of 4-phenyl-2-butanone(yield: 81%). By measurement of the filtrate before purifying withfluorescent X-ray measurement, it was affirmed that palladium leakagewas not observed from a catalyst composition of the present invention.

A catalyst composition of the present invention filtered off was washedwith tetrahydrofuran, and then recovered by drying under reducedpressure.

It was confirmed by the measurement result using ¹H-NMR and ¹³C-NMR thatthe product obtained is 4-phenyl-2-butanone.

The same operations as described above were repeated 4 times using therecovered catalyst composition of the present invention again as acatalyst. Repeated use times of the catalyst and yield of4-phenyl-2-butanone obtained in each reaction are shown in Table 1.

Experimental Example 3 Hydrogenation Reaction of an Olefin-3

The same reaction as in Experimental Example 1 was conducted except thata catalyst composition of the present invention obtained in Example 3was used instead of the catalyst composition of the present inventionobtained in Example 2. Yields of 4-phenyl-2-butanone obtained are alsorepresented in Table 1.

Comparative Example 1 Hydrogenation Reaction of an Olefin

The same reaction as in Experimental Example 1 was conducted except thata palladium carbon (Pd content: 5%) was used instead of the catalystcomposition of the present invention. Yield of 4-phenyl-2-butanoneobtained is also shown in Table 1. TABLE 1 1st 2nd 3rd 4th 5th time timetime time time Experimental 81% — — — — Example 1 Experimental 93% 80%88% 82% 87% Example 2 Experimental 85% 80% 87% 91% 90% Example 3Comparative 91% — — — — Example 1

In this Table, “-” indicates “not experimented.” (the same in Tableshereinafter).

As clear from Table 1, it is proved that a catalyst composition of thepresent invention has equivalent activity to that of a conventionallyused catalyst, and even by many times repeated use little decrease inactivity was observed.

Example 4 A substitution Reaction at an Allyl Position-1

In the presence of 115 mg of the catalyst composition of the presentinvention (palladium metal content: 0.025 mmol) obtained in Example 1and 26.3 mg of triphenylphosphine, 63.9 mg of allyl methyl carbonate and104.1 mg of dimethyl phenylmalonate were added to 5 ml oftetrahydrofuran, and they were reacted by heating under dry distillationfor 12 hours. After completing the reaction, hexane was added to thereaction solution and stirred. When the reaction solution becametransparent, a catalyst composition of the present invention wasfiltered off. After a filtrate was condensed, it was purified by silicagel thin-layer chromatography to obtain 67.1 mg of dimethylallylphenylmalonate (yield: 54%). By measurement of the filtrate beforepurifying with a fluorescent X-ray spectrometer, no palladium leakagewas observed from a catalyst composition of the present invention.

A catalyst composition of the present invention filtered off was washedwith tetrahydrofuran, and then recovered by drying under reducedpressure.

The same operations as described above were repeated twice using therecovered catalyst composition of the present invention again as acatalyst. Repeated use times of the catalyst and yield of dimethylallylphenylmalonate obtained in each reaction are shown in Table 2.

Example 5 A Substitution Reaction at an Allyl Position-2

In the presence of 231 mg of the catalyst composition of the presentinvention (palladium metal content: 0.025 mmol) obtained in Example 2and 26.3 mg of triphenylphosphine, 63.9 mg of allyl methyl carbonate and104.1 mg of dimethyl phenylmalonate were added to 5 ml oftetrahydrofuran, and they were reacted by heating and dry distillationfor 12 hours. After completing the reaction, hexane was added to thereaction solution and stirred. When the reaction solution becametransparent, a catalyst composition of the present invention wasfiltered off. After a filtrate was condensed, it was purified by silicagel thin-layer chromatography to obtain 109.3 mg of dimethylallylphenylmalonate (yield: 88%). By measurement of the filtrate beforepurifying with a fluorescent X-ray spectrometer, no palladium leakagewas observed from a catalyst composition of the present invention.

A catalyst composition of the present invention filtered off was washedwith tetrahydrofuran, and then recovered by drying under reducedpressure.

The same operations as described above were repeated 4 times using therecovered catalyst composition of the present invention again as acatalyst. A catalyst composition of the present invention did not showpalladium leakage even by the above-described repeated use of 5 times intotal.

Repeated use times of the catalyst and yield of dimethylallylphenylmalonate obtained in each reaction are also shown in Table 2.

Example 6 A Substitution Reaction at an Allyl Position-3

The same reaction as in Example 5 was conducted except that a catalystcomposition of the present invention obtained in Example 3 was usedinstead of the catalyst composition of the present invention obtained inExample 2. Repeated use number of the catalyst and yield of dimethylallylphenylmalonate obtained in each reaction are also shown in Table 2.TABLE 2 1st 2nd 3rd 4th 5th time time time time time Example 4 54% 82%97% — — Example 5 Quant 85% 89% 95% 82% Example 6 95% 100%  94% 94% 71%

As clear from Table 2, it is proved that a catalyst composition of thepresent invention showed little decrease in activity even by many timesof repeated use. Further, it is proved from Example 5 that even by manytimes of repeated use, a catalyst composition of the present inventiondoes not exhibit metal leakage from a polymer carrier.

Example 7 A Substitution Reaction at an Allyl Position-4

The same substitution reaction at an allyl position was conducted as inExample 6, except that a reaction period was 2 hours. And by recoveringthe catalyst used, the same reactions were repeated 5 times. Repeateduse number of the catalyst and yield of dimethyl allylphenylmalonateobtained in each reaction are shown in Table 3. In all of the reactions,metal leakage from a catalyst composition of the present invention wasnot observed. TABLE 3 1st 2nd 3rd 4th 5th time time time time timeExample 7 88% 94% 98% 87% 98%

As clear from Example 7, it is proved that a catalyst composition of thepresent invention obtained in Example 3 has favorable activity eventhough a reaction period is significantly shortened.

Examples 8 to 12 A Substitution Reaction at an Allyl Position

The same substitution reaction at an allyl position was conducted as inExample 7, except that 0.55 mmol of allyl carbonate as described inTable 4 below and 0.50 mmol of a nucleophilic agent as described inTable 4 were used. Compounds obtained in each reaction and yieldsthereof are also shown in Table 4. TABLE 4 Nucleophilic Product Allylcarbonate agent (Amount (Amount of (Amount used) used) yield) Yield Ex.8 ethyl 2- dimethyl dimethyl 2-  94% methylallyl phenyl methylallylphcarbonate malonate enylmalonate (79.3 mg) (104.1 mg) (123.3 mg) Ex. 9allyl methyl carbonate (63.9 mg)

 94% Ex. 10 allyl methyl carbonate (63.9 mg) 1-naphthol  (72.1 mg)

Quant Ex. 11 allyl methyl carbonate (63.9 mg) 2-naphthol  (72.1 mg)

 96% Ex. 12 allyl methyl carbonate (63.9 mg) p-nitrophenol  (69.6 mg)

100%

Generally, it is known that when a nucleophilic agent containing oxygen,such as phenol having an electron accepting group such as a nitro group,and the like, is used, reactivity in a substitution reaction at an allylposition is remarkably decreased. However, As clear from Example 12 inTable 4, it is proved that when a catalyst composition of the presentinvention is used, even when a nucleophilic agent containing oxygen withan electron accepting group, is used, a reaction proceeds extremelyeffectively. From this, it can be understood that a catalyst compositionof the present invention has high catalytic activity as compared with aconventional catalyst.

Example 13 An Oxidation Reaction of an Alcohol

To 5 ml of acetonitrile, 0.025 mmol of the catalyst composition of thepresent invention obtained in Example 3, 67.1 mg of cinnamyl alcohol and63.9 mg of allyl methyl carbonate were added, and they were reactedwhile stirring at 80° C. for 2 hours. After completing the reaction, thecatalyst composition of the present invention was filtered off. After afiltrate was condensed, it was purified by silica gel thin-layerchromatography to obtain 45.4 mg of cinnamaldehyde (yield: 69%). Bymeasurement of the filtrate before purifying with fluorescent X-raymeasurement, palladium leakage was not observed from a catalystcomposition of the present invention.

A catalyst composition of the present invention filtered off was washedwith tetrahydrofuran, and then recovered by drying under reducedpressure.

As clear from Example 13, it is proved that a phosphine ligand does notexist in a reaction system, since by using a catalyst composition of thepresent invention, cinnamyl alcohol is oxidized without inducing asubstitution reaction at an allyl position. That is, it is proved thatin a catalyst composition of the present invention, a triphenylphosphineligand used in synthesis thereof is not contained at all.

INDUSTRIAL APPLICABILITY

A catalyst composition wherein a 0 valence metal catalyst physicallycarried on a crosslinked organic polymer compound, can be obtained byhomogenizing a straight chain organic polymer compound having acrosslinkable functional group and a 0 valence metal catalystcoordinated with a ligand, in a solvent which dissolves these, followedby deposition of the composition produced, and subjecting acrosslinkable functional group in said deposited material to acrosslinking reaction for condensation reacting. Furthermore, thecatalyst composition thus obtained can be safely and easily handledwithout danger of spontaneous ignition, and the like, and is extremelyuseful as a catalyst for various chemical reactions, and further,activity thereof is not lowered by repeated use, and a metal catalystdoes not leak at all from a polymer carrier compound.

1. A catalyst composition comprising a crosslinked organic polymercompound and a palladium catalyst, wherein said catalyst is physicallycarried on said crosslinked organic polymer compound.
 2. The compositionaccording to claim 1, wherein the palladium catalyst is Pd(0) or a saltof Pd(II).
 3. The composition according to claim 2, wherein Pd(0) has noligand.
 4. The composition according to claim 1, wherein the crosslinkedorganic polymer compound is: a crosslinked product of a polymer or acopolymer obtained by polymerizing or copolymerizing 1) at least onekind of a monomer having a crosslinkable functional group and apolymerizable double bond, or a crosslinked product of a copolymerobtained by copolymerizing 1) at least one kind of a monomer having acrosslinkable functional group and a polymerizable double bond and 2) atleast one kind of a monomer having a polymerizable double bond.
 5. Thecomposition according to claim 4, wherein the crosslinked organicpolymer compound is a crosslinked product of a copolymer obtained bycopolymerizing: 1) two kinds of monomers having a crosslinkablefunctional group and a polymerizable double bond and 2) one kind of amonomer having a polymerizable double bond.
 6. The composition accordingto claims 4 or 5, wherein the crosslinkable functional group is an epoxygroup, a carboxyl group, a hydroxyl group, an acyloxyl group, anisocyanato group or an amino group.
 7. The composition according toclaims 4 or 5, wherein ratio of a monomer unit derived from a monomerhaving a crosslinkable functional group and a polymerizable double bondis 0.1 to 100% based on the whole copolymer before crosslinking of thecrosslinked organic polymer compound.
 8. The composition according toclaim 4, wherein 1) the monomer having a crosslinkable functional groupand a polymerizable double bond is represented by: (1) a glycidylcompound having an epoxy group as a crosslinkable functional group,selected from a glycidyl ether or a glycidyl ester represented by thefollowing general formula [1] or [2] respectively,

(wherein R², R³, R⁵ and R⁶ each independently represents a hydrogen atomor an alkyl group having 1 to 6 carbon atoms; X and Y each independentlyrepresents an alkylene group having 1 to 6 carbon atoms; R² may form aring of 3 to 6 members together with carbon atoms of R³ or X, and R⁵ mayform a ring of 3 to 6 members together with carbon atoms of R⁶ or Y; andR¹ and R⁴ each independently is a group represented by the followinggeneral formula [3]:

[wherein R⁷ and R⁸ each independently represents a hydrogen atom or analkyl group having 1 to 6 carbon atoms; R⁹ represents a direct-linkage,an alkylene group having 1 to 6 carbon atoms, an arylene group having 6to 9 carbon atoms, an arylalkylene group having 7 to 12 carbon atoms oran arylenealkylene group having 7 to 15 carbon atoms; and an aromaticring in the above aryl group or aralkyl group may have an alkyl grouphaving 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atomsand/or a halogen atom, as a substituent]); (2) a monomer having acarboxyl group as a crosslinkable functional group, represented by thefollowing general formula [4]:

(wherein R¹⁰ represents a hydrogen atom or an alkyl group having 1 to 6carbon atoms; R¹¹ represents a hydrogen atom, an alkyl group having 1 to6 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkylgroup having 7 to 12 carbon atoms; and an aromatic ring in the abovearyl group or aralkyl group may have an alkyl group having 1 to 4 carbonatoms, an alkoxy group having 1 to 4 carbon atoms and/or a halogen atomas a substituent; and R¹² represents a direct-linkage, an alkylene grouphaving 1 to 6 carbon atoms, an arylene group having 6 to 9 carbon atoms,an arylalkylene group having 7 to 12 carbon atoms or an arylenealkylenegroup having 7 to 15 carbon atoms); and (3) a monomer having a hydroxylgroup, an acyloxy group, an isocyanato group or an amino group as acrosslinkable functional group, represented by the following generalformula [5]:

(wherein R¹³ represents a hydrogen atom or an alkyl group having 1 to 20carbon atoms; R¹⁴ represents a hydroxyl group, an amino group,hydroxyalkyl group having 1 to 50 carbon atoms that may have a carbonylgroup and/or an oxygen atom, a hydroxyaryl group having 6 to 10 carbonatoms, a hydroxyaralkyl group having 7 to 50 carbon atoms that may havea carbonyl group and/or an oxygen atom, a hydroxyalkylaryl group having7 to 50 carbon atoms that may have a carbonyl group and/or an oxygenatom, an acyloxy group having 2 to 6 carbon atoms, an arylacyloxy grouphaving 7 to 15 carbon atoms, an isocyanatoalkyl group having 2 to 7carbon atoms, an isocyanatoaryl group having 7 to 20 carbon atoms, anisocyanatoaralkyl group having 8 to 20 carbon atoms, anisocyanatoalkylaryl group having 8 to 20 carbon atoms, an aminoalkylgroup having 2 to 7 carbon atoms, an aminoaryl group having 7 to 20carbon atoms, an aminoaralkyl group having 8 to 20 carbon atoms or anaminoalkylaryl group having 8 to 20 carbon atoms; an aromatic ring inthe above hydroxyaryl group, hydroxyaralkyl group, hydroxyalkylarylgroup, arylacyloxy group, isocyanatoaryl group, isocyanatoaralkyl group,isocyanatoalkylaryl group, aminoaryl group, aminoaralkyl group andaminoalkylaryl group may have an alkyl group having 1 to 4 carbon atoms,an alkoxy group having 1 to 4 carbon atoms and/or a halogen atom; R¹⁵represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7to 12 carbon atoms; and an aromatic ring in the above aryl group oraralkyl group may have an alkyl group having 1 to 4 carbon atoms, analkoxy group having 1 to 4 carbon atoms and/or a halogen atom, as asubstituent), and 2) the monomer having a polymerizable double bond isrepresented by the general formula [6]:

(wherein R¹⁶ and R¹⁷ each independently represent a hydrogen atom or analkyl group having 1 to 6 carbon atoms; R¹⁹ represents a hydrogen atom,a halogen atom or an alkyl group having 1 to 6 carbon atoms; R¹⁸represents a carboxyl group, a hydroxyl group, an acyloxy group having 2to 6 carbon atoms, an arylacyloxy group having 7 to 15 carbon atoms, analkoxycarbonyl group having 2 to 6 carbon atoms, an alkyl group having 1to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms and anaralkyl group having 7 to 12 carbon atoms; an aromatic ring in the abovearylacyloxy group, aryl group and aralkyl group, may have further analkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4carbon atoms or a halogen atom, as a substituent).
 9. The compositionaccording to claim 8, wherein: one kind of the monomer having acrosslinkable functional group and a polymerizable double bond is aglycidyl ether represented by the general formula [1]; and the otherkind thereof is a monomer represented by the general formula [4]containing a carboxyl group, as a crosslinkable functional group, or amonomer represented by the general formula [5] containing a hydroxylgroup as a crosslinkable functional group.
 10. The composition accordingto claim 8, wherein at least one kind of monomers having a crosslinkablefunctional group and a polymerizable double bond represented by thegeneral formulas [1], [2], [4] and [5], and monomers having apolymerizable double bond represented by the general formula [6], is onehaving an aromatic ring.
 11. The composition according to claim 8,wherein all of monomers having a crosslinkable functional group and apolymerizable double bond represented by the general formulas [1], [2],[4] and [5], and of monomers having a polymerizable double bondrepresented by the general formula [6], are those having an aromaticring.
 12. The composition according to claim 8, wherein in a monomercontaining a hydroxyl group as a crosslinkable functional group,represented by the general formula [5], R¹⁴ is a straight chainhydroxyalkyl group having 1 to 50 carbon numbers, which may contain anoxygen atom.
 13. The composition according to claim 4, wherein in thecrosslinked organic polymer compound, the shortest number of atoms ofcrosslinked portion exiting between an alkylene chain derived from apolymerizable double bond and another alkylene chain derived from apolymerizable double bond is 1 to
 400. 14. The composition according toclaim 1, wherein the crosslinked organic polymer compound is thatobtained by crosslinking a copolymer of: (1) a glycidyl compound havingan epoxy group and a polymerizable double bond; (2) a styrene typemonomer; and (3) an acrylic acid type monomer or a monomer containing ahydroxyalkyl group having at least one oxygen atom and a polymerizabledouble bond.
 15. The composition according to claim 14, wherein themonomer of (3) in the crosslinked organic polymer compound is acopolymer of a monomer having a hydroxyalkyl group containing at leastone oxygen atom and a polymerizable double bond.
 16. The compositionaccording to claim 14, wherein: the glycidyl compound having an epoxygroup and a polymerizable double bond is vinylbenzyl glycidyl ether orvinyl phenylglycidyl ether; the styrene type monomer is styrene ormethylstyrene; the acrylic acid type monomer is an acrylic acid or amethacrylic acid; and the monomer containing a hydroxyalkyl group havingat least one oxygen atom and a polymerizable double bond istetraethylene glycol monomethacryloyl ester or tetraethylene glycolmono-2-phenyl-2-propenyl ether.
 17. A method for producing thecomposition according to claim 1, characterized in that: a straightchain organic polymer compound having a crosslinkable functional group,and a palladium catalyst are homogenized in a solvent which dissolvessaid straight chain organic polymer compound; followed by depositing thecomposition produced; and subjecting a crosslinkable functional group insaid deposited composition to a crosslinking reaction.
 18. The methodfor production according to claim 17, wherein the palladium catalyst isa complex with triphenylphosphine, tri-t-butylphosphine,triethylphosphine, or trimethylphosphine.
 19. A method for substitutionreaction at an allyl position, characterized in that an allyl carbonateand a nucleophilic agent are reacted in the presence of the compositionaccording to claim
 1. 20. A method for oxidization reaction of analcohol, characterized in that the composition according to claim 1 isreacted with an alcohol.